Structure Property

Relationship of Polymer
1.
Solubility
• Solubility is the ability of a polymer to dissolve in a solvent.
• Solubility change with change in polymer structure.
– Increases with short branch
– Decreases with long branch
– Decreases with crosslinking

Crosslinked polymer
2. Glass Transition Temperature
(Tg)
• The temperature at which a polymer transitions from a hard,
glassy material to a soft, rubbery material.
Tg decreases with Chain
Flexibility
• Tg depends on the ability of a chain to undergo internal
rotations.
• Higher the freedom of rotation, the more flexible are the
chains.
• Linear polymers with single bonds have high degree of
rotation.
• The presence of aromatics, cyclic structures in backbone
hinder this rotation.
Tg decreases with big bulky side
groups
• Big bulky side groups can lower the Tg
• The big side groups limit how closely the polymer chains can
pack together. The further they are from each other, the more
easily they can move around.
• We can see this with a series of methacrylate polymers
Tg increase with Cross-
linking
• cross-linking increases Tg since
• The presence of covalent bonding between chains reduces
molecular freedom
Tg = -93 °C

Tg= 50 °C
Tg decreases with
Plasticizer
• Plasticizers are small molecules which occupy position
between polymer chains
• To increase flexibility, elongation and to reduce
hardness
 3. Thermal stability
• Thermal stability is the stability of a polymer at high temperatures.
• Aromatic cyclic chains are more stable than aliphatic
carbon chains at elevated temperatures.
• Polyvinyl fluoride and PVDF are more stable to elevated temperatures than the
corresponding chloride polymers. polytetrafluoroethylene (PTFE) is highly stable.

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•
• Presence of an oxygen or a sulfur atom in the backbones such as polyphenylene oxide (PPO),
polyphenylene sulfide (PPS), and polyphenylene sulfone are highly stable at elevated temperatures.
4. Tensile
strength
• The tensile strength of a polymer quantifies how much stress
the polymer will endure before failing.
• Tensile strength changes with change in polymer structure.
• Branched< Linear< Crosslinked
Reference
s
• Raymond B. Seymour & Charles E. Carraher, Jr; Structure-
Property Relationships in Polymers
• http://www.socoolglasses.com/definition-of-glass-transition-
temperature/
• http://pslc.ws/macrog/tg.htm
• http://chemistry.tutorvista.com/analyticalchemistry/homopol
ymer.html