Physical crosslinking effects in α,ω-dihydroxy terminated polybutadienes

Structure and molecular dynamics of α,ω-dihydroxy terminated polybutadienes of varying number averaged molecular weight (1320-10 500 g/mol) have been investigated by Fourier-transformed infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). DSC and DRS revealed an increase in the glass transition temperature upon decrease of the molecular weight, accompanied by an increasing dynamic fragility m (or steepness index) of the dielectric α-process. This correlation between Tg and m for different molecular weights indicates the presence of a physical network, where H-bonded end-group clusters act as temporary crosslinks. From the dielectric relaxation strength Δɛα(Mn), the fraction of associated hydroxy groups (fbond) was estimated showing a peak value for the two but shortest polymers, a behaviour that strongly resembles the molecular weight dependence of the fragility. By considering the quantity fbond(Mn) in a modified Fox-Flory approach, the measured Tg(Mn) behaviour could be reproduced in a satisfying way. FTIR results support this general picture and show a considerable dependence of the extent of hydrogen bonding and formation of hydroxy groups associates on the molecular weight. Further, WAXS and DSC results disprove the idea of formation of pseudo-crystalline hydrophobic microdomains in these compounds as suggested by other authors.