Thermal Properties of

Polymers + Condensation
polymerization
Definition of Terms: 2

Glassy State
• State in the amorphous region of the polymer, the molecules of
the polymer are in a frozen state, where the molecules can
vibrate slightly but are not able to move significantly.
• Crystalline state is more favored, greater Van der Waal
interactions in polymer chain.
• In this state, the polymer is brittle, hard and rigid analogous to
glass.
• When polymers are in temperatures below their Tg (Glass
Transition Temperature) considered to be in its glassy state.
• Bends to accommodate strain
Definition of Terms: 3

Rubbery State
• In the amorphous region of the polymer, when the polymer is
heated, the polymer chains are able to wiggle around each other,
and the polymer becomes soft and flexible similar to rubber due
to increase in temperature.
• Viscoelastic
• Weaker Van der Waals interactions, generally low Young's
modulus and high failure strain when compared to glassy state.
• When polymers are in temperatures above their Tg (Glass
Transition Temperature) considered to be in its rubbery state.
Definition of Terms: 4

Glass Transition Temperature (Tg)

• The temperature at which the glassy state makes a transition
to rubbery state
• The glass transition occurs only in the amorphous region, and
the crystalline region remains unaffected during the glass
transition in the semi-crystalline polymer.
• It is always lower than the melting temperature (Tm) of the
crystalline state of the material
• The transition is not considered a phase transition
 5

Melting Point and

Glass Transition
Temperature
 Tg – Second Order Transition 6

Tm – First Order Transition

• The glass transition temperature is the property of the

amorphous region of the polymer, whereas the crystalline region is
characterized by the melting point.
• The difference between first and second order phase transition is
that in first order phase transition entropy, volume and
energy of the thermodynamic system change abruptly whereas
in second order phase transition it changes continuously.
• The semi-crystalline polymer shows both the transitions
corresponding to their crystalline and amorphous regions
 7

• Thus, the semi-crystalline polymers have true melting

temperatures (Tm) at which the ordered phase turns to
disordered phase, whereas the amorphous regions soften over a
temperature range known as the glass transition (Tg).
• Amorphous polymers do not possess the melting point, but all
polymers possess the glass transition temperature.

Presence of double bonds, Defects caused by

Melting Point
Melting Point

aromatic groups, bulky or branching chains

large side groups
(High Molecular Weight)
8
9
 10

Factors Affecting the

Glass Transition
Temperature
 11
• The glass transition temperature depends on the mobility and
flexibility (ease of the chain segment to rotate along the chain
backbone) of the polymeric chains.

Restricted mobility Free movement of

of polymer chains polymer chains
I. Intermolecular Forces 12

• Strong intermolecular forces cause higher Tg

II. Chain Stiffness

• The presence of the stiffening groups in the polymer chain
reduces the flexibility of the chain, leading to higher glass
transition temperature.
III. Cross-Linking.
• The cross-links between chains restrict rotational motion
and raise the glass transition temperature. Hence, higher
cross-linked molecule will show higher Tg than that with
lower cross-linked molecule.
IV. Pendant groups 13

• A "pendant" group on a polymer is a small group of atoms

(even a small chain sometimes) that hangs off of the main
chain (that is, the backbone of the polymer).

a.) Bulky pendant groups: the presence of bulky pendant groups can
restrict rotational freedom, leading to higher glass
transition temperature
b.) Flexible pendant groups: the presence of flexible pendant groups
limits the packing of the chains and hence increases the
rotational motion, tending to less Tg value
14
v. Intermolecular Forces 15

• Plasticizers are low molecular weight and non-volatile materials

added to polymers to increase their chain flexibility. They reduce
the intermolecular cohesive forces between the polymer chains,
which in turn decrease Tg.
VI. Molecular Weight
• Tg is increased with the molecular weight. The molecular
weight is related to the glass transition temperature by the
Fox–Flory Equation
• Tg ∞ is the glass transition temperature at the molecular weight 16

of infinity
• K is the empirical parameter called Fox–Flory parameter related
to the free volume inside the polymer
• Mn is number-average molecular weight ( the sum of all molecular
weights divided by their total number)

Thus, glass transition temperature is dependent on free volume, which in

turn is dependent on the average molecular weight of the polymer sample.

Low molecular weight values result in lower glass transition temperatures

whereas increasing values of molecular weight result in an asymptotic
approach of the glass transition temperature to Tg,∞
It is observed that Tg is increased up to the molecular weight of 17

approximately 20 000, and after this limit, the Tg is not

affected appreciably.
 18

Tacticity
 19

• Tacticity is a term used to describe the way pendent groups on a

polymer chain are arranged on a polymer backbone.
• The tacticity of a polymer is determined by what side of the
polymer chain the pendant groups are on, this relative position
can have dramatic effects on the physical properties of the
polymer.
• Tacticity only arises when there is an asymmetric carbon in the
polymer chain backbone usually in free radical polymerization of
vinyl monomers (CH2CHX)
Free radical polymerization 20

Initiation
• Initiation, involves the formation of radicals followed by the
radical's reaction with a vinyl monomer
Propagation
• Propagation is the rapid and progressive addition of monomers to
the growing polymer chain without a change of the active center
Termination
• Termination is the destruction of the growth active center, usually
by combination or coupling of the radicals of two growing polymer
chains or by disproportionation.
 21

ISOTACTIC
• Occurs when the monomer adds to the polymer backbone with the
pendant group on the same as the previous pendant group

SYNDIOTACTIC
• Occurs when the monomer adds where the pendant group adds to
the opposite side of the polymer backbone

ATATIC
• Occurs when there is no order to the way the pendant group adds,
(completely random).
 22

• Isotactic and syndiotactic polymers provide long-range order, which leads

to higher crystallinity in the polymer chain. (High Density)
• Atactic polymers have little order in the polymer backbone and is
amorphous causing lower crystallinity. (Low Density)
23
 24

Condensation
polymerization
 25
• A condensation polymerization is a form of step-growth
polymerization. Functional groups react with each other to form
larger structural units while releasing smaller molecules as a
byproduct, such as water or methanol.

Hydroxyl, Methyl, H2O

Carbonyl, Carboxyl, Aminos, CH3OH
Phosphates, Sulfhydryl

• Condensation polymers form more slowly than addition polymers,

often requiring heat, and they are generally lower in molecular
weight.
26
27
 28

Step-Growth Polymerization
• A stepwise reaction between bi-functional or multi-functional
monomers in which a high-molecular-weight polymer is formed
after a large number of steps.
• Due to the nature of the polymerization mechanism, the reaction
has to proceed for a long time to achieve high molecular weight
polymers.
• The easiest way to visualize the step-growth mechanism is a
crowd of people reaching out to hold their hands to form human
chains — each person has two hands (= two reactive sites).
 29

NOTE: If the
monomers have more
than two reactive
sites branched
polymers are
produced.
 30

POLYAMIDES
• Carboxylic Acid (-COOH) + Amide (RC(O)NR′R″) with a
by-product of H2O
• Held together by Amide Links
• Amides have a carbonyl group attached to a nitrogen atom

POLYESTER
• Alcohol + Carboxylic Acid (-COOH) with a
by-product of H2O
• Held together by Ester Links
 31

TYPE OF MONOMER PRODUCED POLYMER

Bi-functional Bi-functional Linear
Tri-Functional Tetra-Functional Cross-linked
Monomer Reactive Group Terminate Chain

• The average molecular weight and the crosslink density will

depend on the functionality of each monomer involved in the
condensation polymerization and on its concentration in the
mixture.
THANK YOU FOR LISTENING