MODULE 9: POLYMERS → It is common for natural polymers to

have one type of monomer.

CEE11_Pauline Jimenez → E.g.: protein, cellulose, starch, and
natural rubber.
POLYMERS → Cellulose which is part of plants is
composed of sugar molecules (as
→ is a large molecules or
monomers) and as polymers it is
macromolecules with repeated
known as polysaccharide.
subunits (monomer) connected with
→ Natural polymers that have been
each other by chemical bonds. chemically modified are called semi-
MONOMER synthetic polymers such as cellulose
nitrate and cellulose acetate.
→ Is a molecule with low molecular
weight that can bond with another
low molecule to form polymer. MAN-MADE (SYNTHETIC) POLYMERS

ALEXANDER PARKES → can be done in a laboratory or

produced by industrial factories.
→ Treated cellulose with nitric acid and
→ Some examples are nylon (used in our
a solvent which produced
clothes), Teflon (to coat non-stick
nitrocellulose.
cooking utensils) and epoxy resins
→ When nitrocellulose is added with
(used as the binder in countertops or
camphor it produced celluloid that
coatings for floors).
can be used for film industry and a
replacement for ivory.
There are several parameters for
VULCANIZATION
classifications of polymers based on:
→ Process was done when natural
1) Chemical Structures
rubber is treated with sulfur and
applying heat according to British 2) Polymeric Structures
engineer THOMAS HANCOCK (UK
3) Tacticity
patent) and American chemist
CHARLES GOODYEAR. 4) Thermal behavior

5) Molecular forces

CLASSIFICATION OF POLYMERS 6) Methods of synthesis

Polymers can be classified as:

→ Natural CHEMICAL STRUCTURES

→ Semi-synthetic → There are two types of chemical
→ man-made (synthetic) polymers structures namely: homopolymers
and co-polymers.
→ From the name itself, “homo” means
Natural Polymers
the same. Therefore, it means that the
→ occurs naturally which can be found monomer of the polymers is the same
in plants and animals. (A-A-A). While co-polymer means
 combination of two types of which has great strength in term of
monomers (A-B-A-B). density and melting points.
→ The arrangement of copolymers can
be divided into two namely: block
and graft copolymer. Block polymer
has of relatively long sequences of
identical monomeric units. BRANCHED
→ The identical monomers are arranged
→ It has linear polymers with some
linearly. While the graft polymers, the
polymers branched out from it.
long sequence of monomers is
→ This is quite fascinating since it can
attached as branched from the long
have random arrangement and not
chain of polymers.
closely packed.
→ With this arrangement, it does not
Table 1: Comparison of homopolymer and have a solid structure which makes it
co-polymers less density and low melting point.

HOMOPOLYMERS CO-POLYMERS

Formed by Formed by
addition Condensation
polymerization polymerization
Single type of Two types of
monomer monomers
CROSS-LINKED
Often has simple Usually has more
structure complex structure → It is a chemical bond that links
Has one variety Has several varieties between one polymer chain to
another polymer chain forming one
monomeric unit.
→ It has a strong chemical bond which
makes it much stronger and stable.
→ It is very hard for this material to be
recycled.
Examples: PVC, Examples: polyvinyl
polyethylene, acetate, saran,
polypropylene, butadiene rubber
and polystyrene and polyethylene
oxide

TYPE OF POLYMERS
Tacticity
LINEAR
→ The stereochemistry of the
→ It has a long and straight chain. So, arrangement of atoms in polymers.
when combined with several
monomers it can form a long chain
 Three Types of Tacticity: Thermoset

→ isotactic → unlike with thermoplastics materials,

→ syndiotactic while heated it formed cross-linked
→ atactic or heterotactic with other polymer materials such that
the reaction is irreversible. Hence, it
cannot be remolded or reshaped but
Isotactic it can retain its strength and structure
at high temperature.
→ When the substituents are placed on
→ For examples, Bakelite which is use in
the same side of the backbone of the
toasters, handle of pans and pots,
polymers
dishes, electrical outlet, and billiard
balls.
Syndiotactic
Chemical bond holds the atoms together.
→ When the substituents are placed on One type of chemical bond is
alternate position along the intermolecular forces which is quite strong so
backbone of the polymers. that polymers can have strong physical
properties.
Atactic or Heterotactic

→ the substituents are placed on TWO CLASSIFICATIONS OF MOLECULAR

random position along the backbone FORCES
of the polymer.
Elastomers
Backbone of the polymers consists of
→ are “elastic polymers”. So, when we
hydrocarbons.
say elastic, it can be stretched
because it has a rubbery
characteristic, and it can return to its
Two types of Thermal Behavior
original shape.
→ Elastomers is composed of long chain
Thermoplastics polymers with weak intermolecular
forces.
→ like any other polymers materials it is
bonded by intermolecular force (Van Fibers
der Waal’s forces) that can form → is the opposite of elastomers since it
either linear or branched structures. has less elasticity, high tensile strength,
→ These materials when heated are and high melting point.
soften and hardened when it cools → It is woven in a thread - like manner
down. Since it has no interlinking that it has strong intermolecular forces
bond, it can still be remolded or such as hydrogen bond and dipole-
reshaped. dipole interaction.
→ For example, ABS (acrylonitrile → Silk, nylon, polyester, and cotton are
butadiene styrene) which is used in examples of fibers.
musical instruments, Lego brick toys,
and safety hats.
 Polymerization PROPERTIES OF POLYMERS

→ is the process of making monomers There are different variables needed to

into polymers by addition or create the polymer according to your
condensation polymerization. requirements or desired.
→ From the word addition, it simply
→ Such as the monomers to be used
means that it has repeated addition
and reagent or solvents for
of monomer molecules to form
polymerization reaction or cross-
polymers with removing some small
linking the polymer chains.
molecules like water or alcohol.
→ The arrangement of polymers in terms
→ While condensation polymerization,
of structures, stereochemistry of the
group of small molecules have to be
arrangement of atoms, and
removed or eliminated so that the
polymerization can also affect the
monomers can attached to the
properties of polymers such as
backbone of the polymers.
average molecular weight, density,
thermal behavior, and tensile
Addition Polymerization strength.

→ Process initiated by free radical (has

unpaired electron)
TWO ADDITATIVES THAT CAN BE ADDED IN
→ Free radical attacks double bonds to
POLYMERS
form a new free radical.
→ Termination of the reaction occurs Stabilizers
when 2 radicals react to form a bond.
→ can be used to improve the
properties of polymers to resist
Condensation Polymerization oxidation, less sensitive with heat or
light or flame retardants.
→ Monomers combine to form a
polymer and a biproduct.
→ Each time a bond forms between Plasticizers
monomers, small molecules, such as
→ to increase the flexibility, extensibility
water, ammonia, or HCl are
and processability of polymers
“condensed” out.
without altering the chemical
→ The polymerization of nylon:
characteristics.
• For condensation
→ It is often used for the manufacturing
polymerization to occur,
of polyvinyl chloride (PVC).
monomers must be
bifunctional, meaning they
have at least two functional
By computing the degree of polymerization,
groups. we will be able to know how many units of
• If they only had one functional
monomer you need. Now let us represent
group, then only one bond
degree of polymerization with small
would form.
letter n. It should be equal to the molecular
weight of polymer (M) per molecular weight
of a unit of monomer (Mo).
Mathematically, degree of polymerization There are three thermal properties that can
𝑀 describe the response of polymer materials
𝑛=𝑀 namely:
0
→ heat capacity
→ thermal expansion
The strands of polymer molecule can be
→ thermal conductivity.
arranged into two different fashion such as
crystalline and amorphous arrangement.
Heat capacity

→ is the amount of heat that can be

Polymer chains in crystalline arrangement
absorbed by polymer materials.
→ will also be strong and with high
resistance to stress.
Thermal expansion
→ can fold and formed lamellar form.
→ describes the extent a polymer
Polymer chain in amorphous structure
material will expand or contact when
→ disordered arrangement and it makes heated or cooled.
the polymer elastic in property like
thermoplastic materials.
thermal conductivity
If the materials have more crystalline
→ polymer materials act as an insulators
arrangement, then the polymer will be quite
so electrical conductivity is not
strong and less elastic. On the other hand, if
possible.
the thermoplastic materials have more
amorphous arrangement, then it will be
more elastic, and it can easily break with glass transition temperature (Tg).
greater quantity of loads. → When amorphous polymer absorbed
heat, it turns into viscous liquid or
rubbery state and the temperature at
Crystalline Polymer Amorphous this state is called glass transition
Polymer temperature (Tg).
Ordered structure Random structure
Polymer chains can Polymer chains has melting point temperature (Tm)
have syndiotactic atactic polymer → If the polymer continually absorbed
and isotactic chains. thermal energy, then transition of
polymer chains. temperature from glass transition
High density Low density temperature to melting point
High chemical Low chemical temperature (Tm) will occur.
resistance resistance
Higher mechanical Lower mechanical
properties properties
Strong molecular Weak molecular
forces between forces between
polymer chains polymer chains
There are several factors which affect the
glass transition temperature:

Intermolecular forces

→ Polymers with strong molecular forces

such as hydrogen bonds will cause
Tg to increase.
→ Examples are urea and polyurethane
and natural polymer cellulose.

Chain stiffness

→ Polymers that contain small group of

molecules such as amide, sulfone
carbonyl and p-phenylene and
others can increase Tg since it reduces
the flexibility of the polymer chain.

Cross-linking

→ Polymer with cross-linked structure will

increase the Tg value because of
restricted rotational motion. Hence,
polymer with more cross-linked
structure will have higher Tg than
polymer with lesser cross-linked
structure.

Molecular weight

→ The glass transition temperature also

increases with large molecular weight
of the polymer.
→ Polymers with high molecular weight
have less free volume than polymers
with low molecular weight.