Chapter One

Introduction of Polymeric Materials

1.1 General Introduction and Its Scope
Polymers form a very important class of materials without which the life seems
very difficult. They are all around us in everyday use; in rubber, in plastic, in
resins, and in adhesives and adhesives tapes. The word polymer is derived from
greek words, poly= many and mers= parts or units of high molecular mass each
molecule of which consist of a very large number of single structural units
joined together in a regular manner. In other words polymers are giant
molecules of high molecular weight, called macromolecules, which are build up
by linking together of a large number of small molecules, called monomers. The
reaction by which the monomers combine to form polymer is known as
polymerization. The polymerization is a chemical reaction in which two or more
substances combine together with or without evolution of anything like water,
heat or any other solvents to form a molecule of high molecular weight. The
product is called polymer and the starting material is called monomer.

1.2 Historical Development of Polymers

Polymers have existed in natural form since life began and those such as
DNA, RNA, proteins and polysaccharides play crucial roles in plant and animal
life.
From the earliest times, man has exploited naturally-occurring polymers as
materials for providing clothing, decoration, shelter, tools, weapons, writing
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materials and other requirements. However, the origin of today’s polymer
industry is commonly accepted as being the nineteenth century when important
discoveries were made concerning the modification of certain natural polymers.
In eighteenth century, Thomas Hancock gave an idea of modification of natural
rubber through blending with certain additives. Later on, Charles Goodyear
improved the properties of natural rubber through vulcanization process with
sulfur. The Bakelite was the first synthetic polymer produced in 1909 and was
soon followed by the synthetic fiber, rayon, which was developed in 1911. The
systematic study of polymer science started only about a century back with the
pioneering work of Herman Staudinger. Staudinger has given a new definition
of polymer. He in1919 first published this concept that high molecular mass
compounds were composed of long covalently bonded molecules.

1.3 Classification of Polymers

Polymer is a generic name given to a vast number of materials of high molecular
weight. These materials exist in countless form and numbers because of very
large number and type of atoms present in their molecule. Polymer can have
different chemical structure, physical properties, mechanical behavior, thermal
characteristics, etc., and on the basis of these properties polymer can be
classified in different ways, which are summarized in Table 1.1, whereas,
important and broad classification of polymers are described in the next section.

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A. NATURAL VS. SYNTHETIC
Polymers may either be naturally occurring or purely synthetic. All the
conversion processes occurring in our body (e.g., generation of energy from our
food intake) are due to the presence of enzymes. Life itself may cease if there is
a deficiency of these enzymes. Enzymes, nucleic acids, and proteins are
polymers of biological origin. Their structures, which are normally very
complex, were not understood until very recently. Starch — a staple food in
most cultures — cellulose, and natural rubber, on the other hand, are examples
of polymers of plant origin and have relatively simpler structures than those of
enzymes or proteins. There are a large number of synthetic (man-made)

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polymers consisting of various families: fibers, elastomers, plastics, adhesives,
etc. Each family itself has subgroups.

B. POLYMER STRUCTURE
1. Linear, Branched or Cross-linked, Ladder vs. Functionality
As we stated earlier, a polymer is formed when a very large number of structural
units (repeating units, monomers) are made to link up by covalent bonds under
appropriate conditions. Certainly even if the conditions are ―right‖ not all simple
(small) organic molecules possess the ability to form polymers. In order to
understand the type of molecules that can form a polymer, let us introduce the
term functionality.
The functionality of a molecule is simply its interlinking capacity, or the number
of sites it has available for bonding with other molecules under the specific
polymerization conditions. A molecule may be classified as monofunctional,
bifunctional, or polyfunctional depending on whether it has one, two, or greater
than two sites available for linking with other molecules. For example, the extra
pair of electrons in the double bond in the styrene molecules endows it with the
ability to enter into the formation of two bonds. Styrene is therefore
bifunctional. The presence of two condensable groups in both
hexamethylenediamine (–NH2) and adipic acid (–COOH) makes each of these
monomers bifunctional. However, functionality as defined here differs from the
conventional terminology of organic chemistry where, for example, the double
bond in styrene represents a single functional group. Besides, even though the
interlinking capacity of a monomer is ordinarily apparent from its structure,

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functionality as used in polymerization reactions is specific for a given reaction.
A few examples will illustrate this.
A diamine like hexamethylenediamine has a functionality of 2 in amide-forming
reactions such as that shown in Equation 1.2. However, in esterification
reactions a diamine has a functionality of zero.
Butadiene has the following structure:

The structural units resulting from the reaction of monomers may in principle be
linked together in any conceivable pattern. Bifunctional structural units can
enter into two and only two linkages with other structural units. This means that
the sequence of linkages between bifunctional units is necessarily linear. The
resulting polymer is said to be linear. However, the reaction between
polyfunctional molecules results in structural units that may be linked so as to
form nonlinear structures. In some cases the side growth of each polymer chain
may be terminated before the chain has a chance to link up with another chain.
The resulting polymer molecules are said to be branched.
In other cases, growing polymer chains become chemically linked to each other,
resulting in a cross-linked system (Figure 1.2).
The formation of a cross-linked polymer is exemplified by the reaction of epoxy
polymers, which have been used traditionally as adhesives and coatings and,

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more recently, as the most common matrix in aerospace composite materials.
Epoxies exist at ordinary temperatures as low-molecular-weight viscous liquids
or prepolymers. The most widely used prepolymer is diglycidyl ether of
bisphenol A (DGEBA), as shown below (15):

The transformation of this viscous liquid into a hard, cross-linked three-

dimensional molecular network involves the reaction of the prepolymer with
reagents such as amines or Lewis acids. This reaction is referred to as curing.
The curing of epoxies with a primary amine such as hexamethylenediamine
involves the reaction of the amine with the epoxide. It proceeds essentially in
two steps:
1. The attack of an epoxide group by the primary amine

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2. The combination of the resulting secondary amine with a second epoxy group
to form a branch point (19).

The presence of these branch points ultimately leads to a cross-linked infusible

and insoluble polymer with structures such as (20).

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Polystyrene (2), polyethylene (21), polyacrylonitrile (22), poly (methyl
methacrylate) (23), and poly (vinyl chloride) (24) are typical examples of linear
polymers.

Ladder polymers constitute a group of polymers with a regular sequence of

cross-links. A ladder polymer, as the name implies, consists of two parallel
linear strands of molecules with a regular sequence of crosslinks.

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Ladder polymers have only condensed cyclic units in the chain; they are also
commonly referred to as double-chain or double-strand polymers.

Example 1.1:
Show the polymer formed by the reaction of the following monomers. Is the
resulting polymer linear or branched/cross-linked?

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2. Amorphous or Crystalline
Structurally, polymers in the solid state may be amorphous or crystalline. When
polymers are cooled from the molten state or concentrated from the solution,
molecules are often attracted to each other and tend to aggregate as closely as
possible into a solid with the least possible potential energy. For some polymers,
in the process of forming a solid, individual chains are folded and packed
regularly in an orderly fashion. The resulting solid is a crystalline polymer with
a long-range, three-dimensional, ordered arrangement. However, since the
polymer chains are very long, it is impossible for the chains to fit into a perfect
arrangement equivalent to that observed in low-molecular-weight materials. A
measure of imperfection always exists. The degree of crystallinity, i.e., the
fraction of the total polymer in the crystalline regions, may vary from a few
percentage points to about 90% depending on the crystallization conditions.
Examples of crystalline polymers include polyethylene (21), polyacrylonitrile
(22), poly (ethylene terephthalate) (28), and polytetrafluoroethylene (29).

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In contrast to crystallizable polymers, amorphous polymers possess chains that
are incapable of ordered arrangement. They are characterized in the solid state
by a short-range order of repeating units.These polymers vitrify, forming an
amorphous glassy solid in which the molecular chains are arranged at random
and even entangled. Poly (methyl methacrylate) (23) and polycarbonate (30) are
typical examples.

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3. Homopolymer or Copolymer
Polymers may be either homopolymers or copolymers depending on the
composition. Polymers composed of only one repeating unit in the polymer
molecules are known as homopolymers. However, chemists have developed
techniques to build polymer chains containing more than one repeating unit.
Polymers composed of two different repeating units in the polymer molecule are
defined as copolymers. An example is the copolymer (32) formed when styrene
and acrylonitrile are polymerized in the same reactor. The repeating unit and the
structural unit of a polymer are not necessarily the same. As indicated earlier,
some polymers such as nylon 6, 6 (5) and poly (ethylene terephthalate) (28)
have repeating units composed of more than one structural unit. Such polymers
are still considered homopolymers.

The repeating units on the copolymer chain may be arranged in various degrees
of order along the backbone; it is even possible for one type of backbone to have
branches of another type. There are several types of copolymer systems:

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• Random copolymer — the repeating units are arranged randomly on the chain
molecule. It we represent the repeating units by A and B, and then the random
copolymer might have the structure shown below:

• Alternating copolymer — there is an ordered (alternating) arrangement of the

two repeating units along the polymer chain:

• Block copolymer — the chain consists of relatively long sequences (blocks)

of each repeating unit chemically bound together:

• Graft copolymer — Sequences of one monomer (repeating unit) are ―grafted‖

onto a backbone of the another monomer type:

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4. Fibers, Plastics, or Elastomers
Polymers may also be classified as fibers, plastics, or elastomers. The reason for
this is related to how the atoms in a molecule (large or small) are hooked
together. To form bonds, atoms employ valence electrons. Consequently, the
type of bond formed depends on the electronic configuration of the atoms.

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Depending on the extent of electron involvement, chemical bonds may be
classified as either primary or secondary.
In primary valence bonding, atoms are tied together to form molecules using
their valence electrons. This generally leads to strong bonds. Essentially there
are three types of primary bonds: ionic, metallic, and covalent. The atoms in a
polymer are mostly, although not exclusively, bonded together by covalent
bonds.
Secondary bonds on the other hand, do not involve valence electrons. Whereas
in the formation of a molecule atoms use up all their valence bonds, in the
formation of a mass, individual molecules attract each other. The forces of
attraction responsible for the cohesive aggregation between individual molecules
are referred to as secondary valence forces. Examples are van der Waals,
hydrogen, and dipole bonds. Since secondary bonds do not involve valence
electrons, they are weak. (Even between secondary bonds, there are differences
in the magnitude of the bond strengths: generally hydrogen and dipole bonds are
much stronger than van der Waals bonds.) Since secondary bonds are weaker
than primary bonds, molecules must come together as closely as possible for
secondary bonds to have maximum effect.
The ability for close alignment of molecules depends on the structure of the
molecules. Those molecules with regular structure can align themselves very
closely for effective utilization of the secondary intermolecular bonding forces.
The result is the formation of a fiber. Fibers are linear polymers with high
symmetry and high intermolecular forces that result usually from the presence of
polar groups. They are characterized by high modulus, high tensile strength, and

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moderate extensibilities (usually less than 20%). At the other end of the
spectrum, there are some molecules with irregular structure, weak
intermolecular attractive forces, and very flexible polymer chains. These are
generally referred to as elastomers. Chain segments of elastomers can undergo
high local mobility, but the gross mobility of chains is restricted, usually by the
introduction of a few cross-links into the structure. In the absence of applied
(tensile) stress, molecules of elastomers usually assume coiled shapes.
Consequently, elastomers exhibit high extensibility (up to 1000%) from which
they recover rapidly on the removal of the imposed stress. Elastomers generally
have low initial modulus in tension, but when stretched they stiffen. Plastics fall
between the structural extremes represented by fibers and elastomers. However,
in spite of the possible differences in chemical structure, the demarcation
between fibers and plastics may sometimes be blurred. Polymers such as
polypropylene and polyamides can be used as fibers and as plastics by a proper
choice of processing conditions.

C. POLYMERIZATION MECHANISM
Polymers may be classified broadly as condensation, addition, or ring-opening
polymers, depending on the type of polymerization reaction involved in their
formation. Condensation polymers are formed from a series of reactions, often
of condensation type, in which any two species (monomers, dimers, trimers,
etc.) can react at any time leading to a larger molecule. In condensation
polymerization, the stepwise reaction occurs between the chemically reactive
groups or functional groups on the reacting molecules. In the process, a small

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molecule, usually water or ammonia, is eliminated. A typical condensation
polymerization reaction is the formation of polyester through the reaction of a
glycol and a dicarboxylic acid. Examples of condensation polymers include
polyamides (e.g., nylon 6, 6) (5); polyesters (e.g., poly (ethylene terephthalate)
(28); and urea-formaldehyde and phenol–formaldehyde resins.
Addition polymers are produced by reactions in which monomers are added one
after another to a rapidly growing chain. The growing polymer in addition
polymerization proceeds via a chain mechanism. Like all chain reactions, three
fundamental steps are involved: initiation, propagation, and termination.
Monomers generally employed in addition polymerization are unsaturated
(usually with carbon-carbon double bonds). Examples of addition polymers are
polystyrene (2), polyethylene (21), polyacrylonitrile (22), poly (methyl
methacrylate) (23), and poly (vinyl chloride) (24).

D. THERMAL BEHAVIOR
For engineering purposes, the most useful classification of polymers is based on
their thermal (thermo mechanical) response. Under this scheme, polymers are
classified as thermoplastics or thermosets. As the name suggests, thermoplastic
polymers soften and flow under the action of heat and pressure. Upon cooling,
the polymer hardens and assumes the shape of the mold (container).
Thermoplastics, when compounded with appropriate ingredients, can usually
withstand several of these heating and cooling cycles without suffering any
structural breakdown. This behavior is similar to that of candle wax.
Examples of thermoplastic polymers are polyethylene, polystyrene, and nylon.

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A thermoset is a polymer that, when heated, undergoes a chemical change to
produce a cross-linked, solid polymer. Thermosets usually exist initially as
liquids called prepolymers; they can be shaped into desired forms by the
application of heat and pressure, but are incapable of undergoing repeated cycles
of softening and hardening. Examples of thermosetting polymers include urea–
formaldehyde, phenol– formaldehyde, and epoxies.
The basic structural difference between thermoplastics and thermosets is that
thermoplastic polymers are composed mainly of linear and branched molecules,
whereas thermosets are made up of cross-linked systems. Recall from our
previous discussion that linear and branched polymers consist of molecules that
are not chemically tied together. It is therefore possible for individual chains to
slide past one another. For cross-linked systems, however, chains are linked
chemically; consequently, chains will not flow freely even under the application
of heat and pressure.
The differences in the thermal behavior of thermoplastics and thermosets are
best illustrated by considering the change in modulus with temperature for both
polymers (Figure 1.3). At low temperatures, a thermoplastic polymer (both
crystalline and amorphous) exists as a hard and rigid glass. As the temperature is
increased, it changes from a glass to a rubbery elastomer to a viscous melt that is
capable of flowing — hence this phase is also known as the flow region. (The
transitions between the different phases or regions of thermal behavior are
characterized by drops in the magnitude of the modulus — usually two to three
orders. As we shall see later, differences exist between amorphous and
crystalline thermoplastics in the details and nature of these transitions). For the

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thermosetting polymer, on the other hand, the modulus remains high in the
rubbery region, while the flow region disappears.

E. PREPARATIVE TECHNIQUE
Polymers can be classified according to the techniques used during the
polymerization of the monomer.
In bulk polymerization, only the monomer (and possibly catalyst and initiator,
but no solvent) is fed into the reactor. The monomer undergoes polymerization,
at the end of which a (nearly) solid mass is removed as the polymer product. As
we shall see later, bulk polymerization is employed widely in the manufacture of
condensation polymers, where reactions are only mildly exothermic and
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viscosity is mostly low thus enhancing ready mixing, heat transfer, and bubble
elimination. Solution polymerization involves polymerization of a monomer in a
solvent in which both the monomer (reactant) and polymer (product) are soluble.
Suspension polymerization refers to polymerization in an aqueous medium with
the monomer as the dispersed phase. Consequently, the polymer resulting from
such a system forms a solid dispersed phase. Emulsion polymerization is similar
to suspension polymerization but the initiator is located in the aqueous phase
(continuous phase) in contrast to the monomer (dispersed phase) in suspension
polymerization. Besides, in emulsion polymerization the resulting polymer
particles are considerably smaller (about ten times smaller) than those in
suspension polymerization.

F. END USE
Finally, polymers may be classified according to the end use of the polymer. In
this case, the polymer is associated with a specific industry (end use): diene
polymers (rubber industry); olefin polymer (sheet, film, and fiber industries);
and acrylics (coating and decorative materials).

1.4 MOLECULAR WEIGHT

Extremely large molecular weights are observed in polymers with very long
chains. During the polymerization process not all polymer chains will grow to
the same length; this results in a distribution of chain lengths or molecular
weights. Ordinarily, an average molecular weight is specified, which may be
determined by the measurement of various physical properties such as viscosity

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and osmotic pressure. There are several ways of defining average molecular
weight. The number average molecular weight Mn is obtained by dividing the
chains into a series of size ranges and then determining the number fraction of
chains within each size range. The number-average molecular weight is
expressed as:

Where Mi represents the mean (middle) molecular weight of size ranges i, and xi
is the fraction of the total number of chains within the corresponding size range.
A weight-average molecular weight is based on the weight fraction of molecules
within the various size ranges. It is calculated according to

Where, again Mi, is the mean molecular weight within a size range, whereas wi
denotes the weight fraction of molecules within the same size interval.
An alternate way of expressing average chain size of a polymer is as the degree
of polymerization, DP, which represents the average number of repeat units in a
chain. DP is related to the number-average molecular weight Mn by the
equation:

Where m is the repeat unit molecular weight.

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Example 1.2:
What is the molecular weight of polypropylene (PP), with a degree of
polymerization of 3×104?
Solution:
Structure of the repeating unit for PP

Molecular weight of repeat unit = (3*12 + 6*1) = 42

Molecular weight of polypropylene = 3*104*42 = 1.26*106

Example 1.3:
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?
Solution:
We note that Xn and n (DP) define the same quantity for two slightly different
entities. The degree of polymerization for a single molecule is n. But a polymer
mass is composed of millions of molecules, each of which has a certain degree
of polymerization. Xn is the average of these. Thus,
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Where N = total number of molecules in the polymer mass
Mr= molecular weight of repeating unit
ni = DP of molecule i.
Now Mn= Xn*Mr = 100 (15 + 14×10 + 28) = 18,300

EXAMPLE 1.4

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Many polymer properties are affected by the length of the polymer chains. For
example, the melting or softening temperature increases with increasing
molecular weight (for M up to about 100,000 g/mol).At room temperature,
polymers with very short chains (having molecular weights on the order of 100
g/mol) exist as liquids or gases.Those with molecular weights of approximately
1000 g/mol are waxy solids (such as paraffin wax) and soft resins. Solid
polymers (sometimes termed high polymers), which are of prime interest here,
commonly have molecular weights ranging between 10,000 and several million

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g/mol.Thus, the same polymer material can have quite different properties if it is
produced with a different molecular weight. Other properties that depend on
molecular weight include elastic modulus and strength.
Example 1.5:

Below, molecular weight data for a polypropylene material are tabulated.

Compute (a) the number-average molecular weight, (b) the weight-average
molecular weight, (c) the number-average degree of polymerization, and (d) the
weight-average degree of polymerization.

Example 3:

Below, molecular weight data for some polymer are tabulated. Compute (a) the
number average molecular weight, and (b) the weight average molecular weight.
(c) If it is known that this material’s weight-average degree of polymerization is
780, (d) what is this material’s number-average degree of polymerization?

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