Properties and Characterization of Polymers

Polymer Monomers

Homopolymer:

Synthetic (man-made) Polymers:

Natural Polymers:
 Polymer molecules

THE CHEMISTRY OF POLYMER MOLECULES

Hydrocarbon Ethylene (C2H4) → gas at ambient temperature and pressure which
has the following molecular structure:

Under appropriate conditions, ethylene gas reacted, and it will transform to

polyethylene (PE) which is a solid polymeric material. This process begins when an
active center is formed by the reaction between an initiator or catalyst species (R·) and
the ethylene monomer, as follows:

Next, the polymer chain forms by the sequential addition of monomer units to this
actively growing chain molecule which is represented schematically as follows:

After the addition of many ethylene monomer units, the final result is the polyethylene
molecule (Figure 1). Representation of polyethylene chain structure is shown below

or alternatively as

Here, the repeat units are enclosed in parentheses, and the subscript n indicates the
number of times it repeats.
Figure 1. For polyethylene, (a) a schematic representation of repeat unit and chain
structures, and (b) a perspective of the molecule, indicating the zigzag backbone
structure.

Tetrafluoroethylene monomer to form Polytetrafluoroethylene (PTFE) →

Polytetrafluoroethylene (having the trade name Teflon) belongs to a family of

polymers called the fluorocarbons. The vinyl chloride monomer (CH2 = CHCl) is a
slight variant of that for ethylene, in which one of the four H atoms is replaced with
a Cl atom. Its polymerization is represented as:

and leads to poly (vinyl chloride) (PVC),

another common polymer.

Some polymers may be represented using the following generalized

form:

where the R represents either an atom [i.e., H or Cl, for polyethylene or poly(vinyl
chloride), respectively] or an organic group such as CH3, C2H5, and C6H5 (methyl,
ethyl, and phenyl)

(Figure 2). Repeat unit and chain structures for

(a)
polytetrafluoroethylene

(b) poly (vinyl chloride)

(c) polypropylene
Molecular structure of polymers

• Molecular weight and shape of a polymer is not the only basis of its physical
characteristics, the difference in the structure of the molecular chains must also be
considered.
• Table 1. Description and schematic representations of linear, branched,
crosslinked, and network (three-dimensional) molecular structures. Circles
designate individual repeat units

Polymer
Description Figure
Structure

↬ Linear polymers are those in

which the repeat units are joined
together end to end in single
chains.
↬ These long chains are flexible
where each circle represents a
unit.
↬ There may be extensive van der
Waals and hydrogen bonding
between the chains.
↬ Some of the common polymers
that form with linear structures
are polyethylene, poly (vinyl
chloride), polystyrene, poly
(methyl methacrylate), nylon, and
the fluorocarbons.
↬ The chain packing efficiency is
reduced with the formation of
side branches, which results in a
lowering of the polymer density.
↬ For example, high-density
polyethylene (HDPE) is primarily a
linear polymer, whereas low-
density polyethylene (LDPE)
contains short-chain branches.
↬ Adjacent linear chains are joined
one to another at various
positions by covalent bonds.
↬ The process of crosslinking is
achieved either during synthesis
or by a nonreversible chemical
reaction.
 ↬ Often, this crosslinking is
accomplished by additive atoms
or molecules that are covalently
bonded to the chains.
↬ Many of the rubber elastic
materials are crosslinked.
↬ These are multifunctional
monomers forming three or more
active covalent bonds make
threedimensional networks.
↬ A polymer that is highly
crosslinked may also be classified
as a network polymer.
↬ These materials have distinctive
mechanical and thermal
properties; the epoxies,
polyurethanes, and phenol-
formaldehyde belong to this
group.

• Note that polymers may have more than one distinctive structural type, for
example, a linear polymer may have limited branching and crosslinking.

COMMON POLYMERIC MATERIALS

Presently, there are more than 60,000 synthetic polymers known, with this, six types
of polymers (Table 2) account for roughly 75% of those used in both Europe and the
United States.

Polymer Recycle Properties of

Monomer Uses of Polymer
Symbol Polymer

⇢ Translucent if not
Ethylene pigmented.
Bags, films, sheets,
⇢ Soft and flexible.
bubble wrap, toys,
⇢ Unreactive to acids wire insulation.
and bases.
⇢ Strong and tough.

Ethylene Opaque milk, juice,

⇢ Similar to LDPE
detergents, and
⇢ More rigid, shampoo bottles.
tougher, slightly Buckets, crates,
more dense. and fencing
 ⇢ Variable. Rigid if
Rigid: Plumbing
not softened with a
pipe, house siding,
Vinyl chloride plasticizer. Clear
charge cards, hotel
and shiny, but
room keys.
often pigmented.
Softened: Garden
Resistant to most
hoses, waterproof
chemicals,
boots, shower
including oils,
curtains, IV tubing.
acids, and bases.
“Crystal” form:
⇢ Variable. “Crystal”
Food wrap, CD
form transparent,
Styrene cases, transparent
sparkling,
cups.
somewhat brittle.
“Expandable”
⇢ “Expandable” form form: Foam cups,
lightweight foam. insulated
Both forms rigid containers, food
and degraded in packaging trays,
many organic egg cartons,
solvents. packaging peanuts.

Bottle caps.
Propylene ⇢ Opaque, very
Yogurt, cream, and
tough, good
margarine
weatherability.
containers.
High melting point.
Carpeting, casual
⇢ Resistant to oils. furniture, luggage.

⇢ Transparent,
Soft-drink bottles,
Ethylene glycol strong, shatter
clear food
HO – CH2CH2 - OH resistant.
containers,
Terephthalic Acid ⇢ Impervious to acids
beverage glasses,
and atmospheric
fleece fabrics,
gases.
carpet yarns, fiber-
⇢ Most costly of the fill insulation.
six.

THE CHEMISTRY OF POLYMER MOLECULES

• Polymers with very long chains has extremely large molecular weights but during
polymerization process, not all polymer chains will grow to the same length, and
this results in a distribution of chain lengths or molecular weights.

• Usually, an average molecular weight is specified, which can be determined by

the measurement of various physical properties such as viscosity 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 (Figure 3). The number – average molecular weight is expressed as

Equation 1
where Mi represents the mean (middle) molecular weight of size range i, and Xi is
the fraction of the total number of chains within the corresponding size range.

• A weight-average molecular weight Mw is based on the weight fraction of

molecules within the various size ranges. It is calculated according to

Equation 2
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.

• Degree of Polymerization (DP) is an alternative way of expressing average chain

size of a polymer. DP represents the average number of repeat units in a chain,
and it is related to the number-average molecular weight Mn by the equation

Equation 3
where m is the repeat unit molecular weight.

b)
a)
weight fractions of
number
molecules
• The length of polymer chains has affected many polymer properties. For example,
as molecular weight (about 100,000 g/mol) of a polymer increases, its melting or
softening temperature also increases.

• But for polymers with very short chains or having a molecular weight on the order
of 100 g/mol, will usually exist as liquids at room temperature.

• Those with molecular weights of approximately 1000 g/mol exists as waxy solids
(e.g., paraffin wax) and soft resins.

• For polymers with molecular weights ranging between 10,000 and several million
g/mol exist as solid, they are sometimes termed as high polymers.

• Therefore, the same polymer material can acquire various properties if it is

produced with different molecular weight.
THERMOPLASTIC AND Thermosetting POLYMERS

Thermoplastics
•

thermosetting polymers
•

COPOLYMERS
A copolymer is composed of two repeat units as represented in Table 3. It is possible
that there are different sequencing arrangements along the polymer chains which
depends on the polymerization process and the relative fractions of these repeat unit
types. Synthetic rubbers are usually copolymers.

Table 3. Schematic representations of random, alternating, block, and graft

copolymers. The two different repeat unit types are designated by blue and red circles
 COPOLYMER Description Figure

↬ two different units are

randomly dispersed
along the chain

↬ two repeat units

alternate chain
positions

↬ identical repeat units

are clustered in blocks
along the chain

↬ homopolymer side
branches of one type
may be grafted to
homopolymer main
chains that are
composed of a different
repeat unit

Polymer crystallinity ↬

↬
↬

↬
↬