Tyrosine-derived polycarbonates are new carbonate-amide copolymers. Th
ese materials have been suggested for use in medical applications, but
their thermal properties and their enthalpy relaxation kinetics (phys
ical ageing behaviour) have so far not been evaluated in detail. Since
structure-property correlations involving enthalpy relaxation are rar
ely investigated for biomedical polymers, a series of four tyrosine-de
rived polycarbonates was used as a model system to study the effect of
pendant chain length on the thermal properties and the enthalpy relax
ation kinetics. The chemical structure of the test polymers was identi
cal except for the length of their respective pendant chains. This fea
ture facilitated the identification of structure-property correlations
. Quantitative differential scanning calorimetry was utilized to deter
mine the thermal properties and to measure enthalpy relaxation kinetic
s. The glass transition temperature of this family of polymers decreas
ed from 93 to 52 degrees C when the length of the pendant chain was in
creased from two to eight carbon atoms. Successive additions of methyl
ene groups to the pendant chain made a fairly constant contribution to
lowering the glass transition temperature. For pendant chains of four
or more methylene groups, the rate of enthalpy relaxation was indepen
dent of the number of methylene groups in the pendant chain. The entha
lpy relaxation data were fitted to the Cowie-Ferguson model and the re
laxation times obtained were about 90 min. Dynamic mechanical analysis
was employed to study the viscoelastic properties. The available obse
rvations indicate that the polymers become more flexible with increasi
ng length of the pendant chain. The results suggest that the length of
the pendant chain can be used effectively to control important materi
al properties in this series of polymers.