Chain Flexibility

How easily the main chain of the

polymer can move, is a key factor in
determining the properties of the
material.

Factors affecting chain flexibility:

• Temperature
• Types of bonds
• Side groups
• Branching
Chain Flexibility - Temperature
Polymer chains are not static, they are
constantly vibrating and rotating.
How much space or free volume there is
around the chains determines ,how much they
can move.
The more thermal energy (heat) present,
the more the chains will move and the more
space between them. The more flexible the
material.

Each material has a specific temperature at

which the chains are mobile enough that the
material behaves more like a rubbery solid
than a glassy solid. This is the Glass Transition
Temperature (Tg)
Chain Flexibility – Types of Bonds
Single Carbon –Carbon (C-C) and Carbon -
Hydrogen (C-H) bonds move relatively easily.

Double Carbon bonds (C=C) do not rotate

and are very rigid.

Having an Oxygen or a Nitrogen in the main

chain provides additional room for movement
because of the lower number of bonds present
for these atoms.
Chain Flexibility – Types of Bonds
Having a benzene ring in the main chain can
add stiffness to it.
For example: Polycarbonate has two benzene
rings in the main chain separated by a Carbon
with two methyl groups (CH3) attached. This
structure is very rigid. Polyester Has a benzene
ring in the main structure, but also has an
Oxygen and a few Carbon-Hydrogen bonds to
allow it to be flexible when there is adequate
room to move. PET
PC Flexible
Rigid when hot
Chain Flexibility – Side Groups
Side groups restrict chain movement. The
larger the side group, the more rigid the
molecule.

Having a Methyl (CH3) group attached to

one side of the main chain will add some
stiffness. Polypropylene is relatively flexible
even at room temperature.

Having one attached to both sides of

the main chain will add a lot of stiffness.
PMMA is very rigid.
Chain Flexibility – Side Groups
Having a Benzene ring attached to one
side of the chain will greatly affect the
stiffness. Polystyrene is very stiff to the point
of being brittle (CD cases)
Chain Flexibility – Branching
Although branching can increase the
entanglement
of the polymer chains, branching increases the
chain
flexibility.

Larger branches hold the molecules further

apart,
increasing the free volume, giving the
molecules
more room to move.
 Based on the structure of the monomer,
Let us determine some of the polymer’s
properties like:

Crystallinity

Hygroscopic

Glass Transition

Flammability
hylene

•Crystalline – Yes only C-H bonds, flexible

no side groups

• Hygroscopic – No (not O or N)

• Glass Transition – Low (-118⁰ C)

• Flammability – Yes only C-H bonds

pylene

•Crystalline – Yes only C-H bonds,

flexible –side
groups every other C

• Hygroscopic – No (not O or N)

• Glass Transition – Low (-9.44⁰C)

• Flammability – Yes only C-H

bonds
yrene

• Crystalline – No (Benzene ring makes it

too rigid)

• Hygroscopic – No (not O or N)

• Glass Transition – High (99⁰C)

• Flammability – Yes only C-H bonds

inylchloride
• Crystalline – No, rigid (Cl to big to allow)

• Hygroscopic – No (not O or N)

• Glass Transition – High (85⁰C)

• Flammability – No (Cl puts out)

rbonate

• Crystalline – No, too rigid

• Hygroscopic – Yes (O)
• Glass Transition – High (149⁰C)
• Flammability – No (High number of double
carbon bonds will extinguish the
flame)
er (PET)
• Crystalline – Yes, flexible enough

• Hygroscopic – Yes (O)

• Glass Transition – Low (68⁰C)

• Flammability – Yes (only C-H and

C=O bonds)
ide (Nylon 6-6)

• Crystalline – Yes, very flexible

• Hygroscopic – Yes (O and N)
• Glass Transition – Low (57⁰C)
• Flammability – Varies depending on additives, but
will usually self extinguish because of N
Polymethylmethacrylate
(Acrylic)
• Crystalline – No, too rigid (dual methyl

groups)

• Hygroscopic – Yes (O)

• Glass Transition – High (104⁰C)

• Flammability – Yes (only C-H and C=O

bonds)
Polyoxymethylene (Acetal or POM)
• Crystalline – Yes, very flexible
• Hygroscopic – Yes (O)
• Glass Transition – Low (-73⁰C)
• Flammability – Yes (only C and O bonds)
Tg is low for
simple linear
polymers

Tg and Tm
increase with
mer complexity
Basically if a polymer’s glass transition
temperature is well above (say, 50oC above)
ambient room temperature, the material will
behave like a brittle glassy polymer --- it’ll be
stiff with low impact resistance. 

 Conversely, if the Tg is well below room

temperature, the material is what is
commonly termed a rubber or elastomer ---
soft and easily stretched; and those materials
whose Tg is reasonably close to the ambient
temperature will exhibit plastic material
behavior --- strong and tough with good
Molecular weight of polymers

Related to the length of the

chains

Mechanical properties ⇑
with M, but processing
becomes more difficult

Commercial polymers:
large
distribution of
Molecular
weights
Polydispersity index (PDI)
----- ----
Mw / Mn

• Gives information about distribution breadth

• Highly branched polymers : PDI > 20

• Generally (commercial polymers) : 2 < PDI < 20

Mn - can affect brittleness, flow and
compression
properties of the polymer.
Mw -related to strength properties, and
impact resistance
Molecular Weight/Physical Property
Correlations
Property/Process Effect of
s High MW
Effect of
Low MW
Parameter

⇑
Impact Strength
⇑
⇑
Melt Viscosity
⇑ ⇑
Processing Temp
⇑ ⇑
Brittleness
⇑
⇑
Drawability
⇑
Softening Temp
⇑
⇑
Melt Flow
⇑
⇑
Polymer Additives
• Mechanical, chemical, physical Properties can be
modified by additives:
• Fillers
– Improve tensile and compressive strengths, abrasion
resistance,
toughness, and thermal stability
• sand, glass, clay, talc (eg. carbon in tires)
– Particle sizes range from very small (10 nm) to large
(mm)
• Plasticizers: small molecules which occupy positions
between polymer chains (increase distance and
interactions between chains)
– increases flexibility, ductility, and toughness
– reduces hardness and stiffness
• Stabilizers
– UV resistance of C-C bonds
– Oxidation resistance
Structure parameters affecting polymer properties:

Increase of the chain length.

Effect: increase of tensile strength and Modulus of Elasticity (stiffness).

Increase of number and length of side chains.

Effect: increase of tensile strength and stiffness.

Introduction of large monomers in molecules.

Effect: increase of stiffness.

Increase of number and strength of cross-links.

Effect: increase of tensile strength and stiffness.

Orientation of the molecules as a result of deformation during manufacturing.

Effect: anisotropy of the material properties (properties along the deformation
differ from those in other directions).
 CLASSIFICATIONS OF
POLYMERS
According to

Mechanical
response Stress strain Molecular Polymerizatio
origin
to elevated behavior characteristics reaction
temperature
 1- origin

Natural polymers Synthetic polymers

 A) Natural Polymers
• Proteins polyamides of polypeptides
polyisoprenes
• e.g. rubber and gutta-percha
polysaccharides
• e.g. starch , cellulose, agar and
• poly nucleic acids such as DNA
• and RNA.
 B) Synthetic Polymers

Produced in the
laboratory by chemical
reactions. e.g. Acrylic
resin ,nylon and
polystyrene.
 Mechanical responce
To elevated
temperature

Thermoplastic Thermosetting
polymers polymers
 Stress strain behavior

Brittle polymes Plasticpolymers Elastomers

 Molecular
characteristics

shape size chemistry structure

 Molecular
characteristics

1- shape

Straight bent twisted zegzag

 Molecular
characteristics

2- size

Large polymer Small polymer

(high molecular weight) (low molecular weight)
 Molecular
characteristics

3- chemistry

homopolymer copolymer

All monomers of Monomers of tow or more

the same type different types

Random copolymer Alternating copolyme

Graft copolymer
Block copolymer
 Molecular
characteristics

4- structure

Network
linear branched Cross linked
 CLASSIFICATIONS OF POLYMERS

According to

Mechanical
response Stress strain Molecular Polymerizatio
origin
to elevated behavior characteristics reaction
temperature
 5- polymerization
reaction

Condensation
Addition reaction
reaction