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).

1
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.

From the above discussion, it is obvious that the solid states of crystalline and
amorphous polymers are characterized by a long-range order of molecular
chains and a short-range order of repeating units, respectively. On the other
hand, the melting of either polymer marks the onset of disorder. There are,
however, some polymers which deviate from this general scheme in that the
structure of the ordered regions is more or less disturbed. These are known as
liquid crystalline polymers. They have phases characterized by structures
intermediate between the ordered crystalline structure and the disordered
fluid state. Solids of liquid crystalline polymers melt to form fluids in which
much of the molecular order is retained within a certain range of
temperature. The ordering is sufficient to impart some solidlike properties on
the fluid, but the forces of attraction between molecules are not strong enough
to prevent flow. An example of a liquid crystalline polymer is polybenzamide
(31).

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Liquid crystalline polymers are important in the fabrication of lightweight,
ultra-high-strength, and temperature-resistant fibers and films such as
Dupont’s Kevlar

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.

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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:

• Random copolymer — The repeating units are arranged randomly on the

chain molecule. It we represent the repeating units by A and B, then the
random copolymer might have the structure shown below:

AABBABABBAAABAABBA…….(str.24)

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

the two repeating units along the polymer chain:
ABABABABABAB………(str.25)
• Block copolymer — The chain consists of relatively long sequences (blocks)
of each repeating unit chemically bound together:
AAAAA BBBBBBBB AAAAAAAAA BBBB……(str.26)

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• Graft copolymer — Sequences of one monomer (repeating unit) are
“grafted” onto a backbone of the another monomer type:

AAAAAAAAAAAAAAAAAAAAAA
B B
B B
B B
B B
B
B
B
B

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.
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

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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 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
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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 molecule, usually water or ammonia, is eliminated. A
typical condensation polymerization reaction is the formation of a polyester
through the reaction of a glycol and a dicarboxylic acid (Equation 1.8).
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
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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).
As the name suggests, ring-opening polymerization polymers are derived from
the cleavage and then polymerization of cyclic compounds. A broad
generalization of ring-opening polymerization is shown in Equation 1.9.

The nature of the cyclic structure is such that in the presence of a catalyst it
undergoes equilibrium ring-opening to produce a linear chain of degree of
polymerization, n. X is usually a heteroatom such as oxygen or sulfur; it may
also be a group such as lactam or lactone. A number of commercially
important polymers are obtained via ring-opening polymerization. Thus,
trioxane (33) can be polymerized to yield polyoxymethylene (34), the most
important member of the family of acetal resins, and caprolactam (35)
undergoes ring-opening to yield nylon 6 (36), an important textile fiber used
especially for carpets.

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classification of polymers as either condensation or addition polymers as
proposed by Carothers does not permit a complete differentiation between the
two classes or polymers, particularly in view of the new polymerization
processes that have been developed in recent years. Consequently, this
classification has been replaced by the terms step-reaction (condensation) and
chain-reaction (addition) polymerization.
These terms focus more on the manner in which the monomers are linked
together during polymerization.
D. THERMAL BEHAVIOR
For engineering purposes, the most useful classification of polymers is based
on their thermal (thermomechanical) 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,
9
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.

Figure 1.3 Idealized modulus–temperature curves for thermoplastics and

thermosets.

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.

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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 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
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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 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 Figure 1.3
Idealized modulus–temperature curves for thermoplastics and thermosets.

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).

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