POLYMERS

Outcome
At the end of the topic, the students
should be able to:

understand polymerization
identify types of polymerization
classify plastics
understand rubber as polymer
identify miscellaneous polymers
Quizlet

What does poly mean?

Quizlet

poly means many

Quizlet

What does mer mean?

Quizlet

mer means units

Polymerization
Polymers are giants among molecules,
constructed by the sequential
stringing together of smaller
molecules called monomers.
Polymerization
Monomer, a molecule that can react
with other molecules to form
polymers.
Polymerization
For example, polyethylene is a
polymer made from the monomers
ethylene.
Polymerization
For example, polyethylene is a
polymer made from the monomers
ethylene.
Polymerization
Hence, polymerization is any process
in which relatively small molecules,
called monomers, combine chemically
to produce a very large chainlike or
network molecule, called a polymer.
 THE UTILITY OF POLYMERS AND
PLASTICS IN ENGINEERING
APPLICATIONS ARISES FROM THE
FACT THAT MATERIALS CHEMISTS
AND ENGINEERS CAN CONTROL
THEIR PHYSICAL PROPERTIES
The main factors that can be
empirically adjusted to modify
polymers are the:

monomers used,
the type of reactions needed to
generate the polymers, and
the catalysts that are employed to
speed the reactions.

A careful choice of these factors can

ultimately control the physical properties of
the resulting polymer.
Types of Polymerization
 Three Types of
Polymerization

Addition Condensation Co-

polymerization polymerization polymerization
Addition polymerization

Monomers having double or

triple bonds undergo
addition polymerization
without the liberation of
small molecules. The
product polymer is exact
multiple of the original
monomeric molecule e.g.,
polyethylene from
ethylene.
 Three Mechanism of Addition
Polymerization

Free radical Ionic Ziegler-Natta

mechanism mechanism polymerization
Free radical polymerization
INITIATION
The spontaneous decomposition of an
initiator into free radicals.

The next part of initiation involves the

addition of this radical to the monomer
molecule (M) to initiate the chain.
Free radical polymerization
PROPAGATION
The mechanism of propagation is the reaction of the radical M* with its own
monomer M.

Continuous addition of new monomer in this manner will finally produce a

polymer chain in which the substituents are located on alternate atoms.
Free radical polymerization
TERMINATIONS
The most common terminations are the effect of:
i) Collision between two growing chains

(ii) Collision of a growing chain with an initiator radical when the latter is
proportionately in excess.
(iii) Collision between a growing chain with impurities.
Ionic polymerization

It is an important class of addition polymerization but here, instead of free

radicals, the unstable intermediates are either cations or anions.
Ionic polymerization
Ionic polymerization
Coordination or Ziegler-Natta polymerization
The ability to control the specific
configuration of a polymer was first
achieved by Karl Ziegler and Giulio Natta
in the 1950s.

These scientists discovered new catalysts

for the addition polymerization reaction
that increased the rate of reaction and
also controlled the structure.
Coordination or Ziegler-Natta polymerization
The catalysts came to be known as
Ziegler-Natta catalysts. Their discovery
invigorated the study of polymers, and
they were awarded the Nobel prize in
chemistry in 1963 for their efforts.
Coordination or Ziegler-Natta polymerization
It was observed by Ziegler and Natta that in presence of a combination of
transition metal halides (TiCl4, ZrBr3, and halides of V, Zr, Cr, Mo etc.) along with
organometallic compounds (triethyl/trimethyl aluminum) polymerization of
olefins leads to stereospecific polymerization.
Stereospecific polymerization
An organic polymerization in which the spacial arrangements of groups on
asymmetric carbon atoms occur in a regular sequence.
Stereochemistry of Polymers
(i) Isotactic polymers have all the groups in one side of the polymeric backbone
and the monomers are joined in a regular head to tail arrangement.
Stereochemistry of Polymers
(i) Isotactic polymers have all the groups in one side of the polymeric backbone
and the monomers are joined in a regular head to tail arrangement.
Stereochemistry of Polymers
(ii) Syndiotactic polymers have similar head to tail arrangements but here Y
groups appear on opposite sides of polymer backbone alternately.
Stereochemistry of Polymers
(iii) Atactic polymers have Y groups arranged randomly along the polymeric
backbone and the material is soft, elastic, rubbery.
Stereochemistry of Polymers
Here we see polypropylene,

The large purple balls here represent

those methyl groups. In (a), all of the
methyl groups are arranged on the same
side of the polymer chain, giving
isotactic polypropylene.

In (b), the methyl groups are on alternate

sides of the chain, making syndiotactic
polypropylene.

Finally, the random arrangement of the

methyl groups in (c) is atactic
polypropylene.
Condensation Polymerization

Combination through
different functional groups
of monomers with
elimination of small
molecules like H2O.
Condensation Polymerization

a.k.a. Nylon or polyamide

Condensation Polymerization

a.k.a. polyester
Nylon or polyamide Products
Dacron or polyester Products
 Copolymerization

Two or more monomers

undergoing joint
polymerization is called
copolymerization reaction
such as the production of
SBR (Styrene butadiene
rubber).
Copolymerization
Degree of Polymerization

The number of repeating units in a polymer.

PLASTICS
(RESINS)
PLASTICS (RESINS)
Plastics are a class of high
polymers which can be
molded into any desired
form by heat and pressure.
Resins are actually the
binders used for plastics
and these two terms are
used synonymously.
 PLASTICS (RESINS)

There are two classes of plastics or

resins:

1.Thermoplastic resins

These plastics soften on heating and

harden on cooling and this change is
not chemical but physical in nature,
hence repeated heating and cooling
also does not alter its nature.
 PLASTICS (RESINS)

1.Thermoplastic resins

The deformation upon heating may

seem like a weakness because it
means that they are not suitable for
high temperature applications.
 PLASTICS (RESINS)

1.Thermoplastic resins

But most plastic objects, including

children’s toys and plastic bottles,
are generally used at ambient
temperatures. Hence, the melting
when heated appreciably is not a
major drawback.
 PLASTICS (RESINS)

2. Thermosetting resins

These are those which are heated during

molding and heating is continued until set
and hardened. This hardened material
cannot be softened again, hence the setting
is permanent and irreversible.
 PLASTICS (RESINS)

2. Thermosetting resins

These polymers can maintain their shape

and strength when heated. The name
“thermosetting” comes from the fact that
these polymers must be heated to set or
“lock in” their structures. But once this has
been done, the materials offer increased
strength and do not lose their shape upon
further heating.
The different properties of thermoplastic and thermosetting
polymers result from the ways in which the polymer chains
interact with one another.
 Crosslinks

Chemically, these cross-links are

additional covalent bonds that join
the polymer chains to one another.
Like most covalent bonds, they are
strong enough that they do not
readily fail upon heating. So the
cross-linked polymer keeps its
shape.
 Crosslinks

An important example of the

engineering importance of cross-
linking in American industrial
history is the discovery of
vulcanization. In vulcanization,
natural rubber is heated in the
presence of sulfur. This produces
cross-linking and leads to a harder
material that is markedly more
resistant to heat.
 Natural Rubber

Until vulcanization was discovered,

natural rubber was difficult to use
in applications such as automobile
tires because it would become
sticky when heated.

Natural rubber is no longer widely

used, having been replaced by
synthetic forms.