The thermodynamics of polymerisation of aldehydes and cyclic ethers. Part II. Tetrahydrofuran and 1.3 dioxolan

Abstract

Abstract The equilibrium between gaseous monomer and amorphous polymer has been studied for tetrahydrofuran and 1.3‐dioxolan between 40 and 80°C. The approach to equilibrium catalysed by cationic initiators was extremely slow for tetrahydrofuran but rapid for 1.3‐dioxolan. From the equilibrium pressures of monomer the ΔH 0 gc and ΔS 0 gc values have been calculated. By means of thermodynamic data for the vaporisation of the two monomers, obtained from vapour pressure measurements, we have also calculated ΔH 0 1c and ΔS 0 1c . For tetrahydrofuran: ΔH 0 gc (298°K) = −39.7 ± 2.3 kJ · mole −1 ; ΔH 0 1c (298°K) = −7.4 ± 2.3 kJ · mole −1 ; ΔS 0 gc (298°K) = −111.6 ± 6.9 J ·°K −1 mole −1 ; ΔS 0 1c (298°K) = −16.2 ± 7.0 J ·°K −1 mole −1 ; and for 1.3‐dioxolan: ΔH 0 gc (298°K) = −50.1 ± 0.8 kJ · mole −1 ; ΔH 0 1c (298°K) = −14.6 ± 1.0 kJ · mole −1 ; ΔS 0 gc (298°K) = −139.2 ± 2.2 J ·°K −1 mole −1 ; ΔS 0 1c (298°K) = −36.7 ± 3.0 J ·°K −1 mole −1 ;