Thermal and mechanical characterization of poly[bis(4-benzylphenoxy)phosphazene

Abstract

In this paper we report the thermal and mechanical characterization of poly[bis(4-benzylphenoxy)phosphazene] (PBPP). Glass transition and melting temperatures of 13.8 and 88.2°C respectively, and heat of fusion of 7.0 J g −1 were measured by differential scanning calorimetry (d.s.c.) for the as-synthesized polymer. Crystallization studies from the melt, in both isothermal and dynamic regimes, showed a low crystallizability of PBPP, due to the high mobility and steric hindrance of lateral substituents, with a heat of fusion no higher than 9 J g −1. Activation energies of about 70 kJ mol −1 were calculated both for the crystallization process and for the rubber-glass transition in the amorphous state. The highest crystallization rate in isothermal experiments occurred at a temperature of 45°C. Thermodegradation of PBPP in air was found to start with the probable formation of the hydroperoxide group on the methylene site at about 233°C, as demonstrated from both thermogravimetric and d.s.c. analyses. PBPP film behaved as an elastomeric polymer with a strain at break higher than 350%. A tensile modulus of 1.2 MPa and a stress at break of 4.8 MPa for the amorphous polymer were measured, whereas crystalline polymers exhibited higher tensile modulus and stress at break, ranging from 34 to 48 MPa and from 7 to 12 MPa, respectively.