Polymer melting and thermodynamics of fusion

Tf

We can understand the Tf of real polymers by considering the free energy of fusion: G f = H f Tf Sf = 0 Tf is determined by the relative changes in enthalpy and entropy in going from the crystalline state to the amorphous state. Tf = H f Sf
GCH 6101- Polymer states of matter: crystalline state PM Wood-Adams 1

Melting point depressions

Results from the presence of impurities In polymers non-crystallisable comonomers, chain ends and solvents (or plasticizers) all act as impurities Melting point depression is given by:

melting point in the absence of impurities

1 1 R 0 = XB Tf Tf H f
XB = 2M 0 MN

mole fraction impurity

Effect of chain ends: Effect of solvent:

XB =

Vu 1 V1

where Vu = molar volume of mer units and V1= molar volume of solvent, 1 = volume fraction solvent. Molar volumes are calculated from molar mass and density.
GCH 6101- Polymer states of matter: crystalline state PM Wood-Adams 2

Aspects of chemical structure that effect Tf

Structural regularity Bond flexibility Close packing ability Strong inter-chain attraction We will consider some examples of these effects.

GCH 6101- Polymer states of matter: crystalline state

PM Wood-Adams

Effect of regularity and size

Consider polyesters with the general formula:

The nature of R has an enormous effect on Tf:

The propylene group is atactic i.e. irregular

GCH 6101- Polymer states of matter: crystalline state PM Wood-Adams 4

Effect of flexibility
Consider polyesters with the general formula shown below where the group R has a large effect on Tf.

GCH 6101- Polymer states of matter: crystalline state

PM Wood-Adams

Effect of inter-chain attraction

Consider aromatic polyesters with the general formula shown below where the group R has a large effect on Tf.

increasing polarity

GCH 6101- Polymer states of matter: crystalline state

PM Wood-Adams

Length scales in polymer structure

GCH 6101- Polymer states of matter: crystalline state

PM Wood-Adams