Journal of Polymer Science Part B: Polymer Physics, Vol.34, No.6, 1031-1054, 1996
Concept of Hard Clusters in the Interpretation of Thermal and Mechanical-Properties of Polyurethane and Polyurethane Acrylate Networks
Polyurethane (PU) and polyurethane acrylate (PUA) networks based on hydroxyl-terminated polycaprolactone (PCL), 1,3-bis-2,2’(2-isocyanatopropyl)benzene (m-TMXDI), trimethylolpropane (TMP) for PU or hydroxyethyl methacrylate (HEMA) for PUA were synthesized. Glass transition temperature, T-g, dynamic mechanical relaxation, alpha, and equilibrium tensile modulus, E’, were measured to compare the two kinds of networks. To explain thermal and mechanical properties of networks, the concept of hard clusters has been introduced. PU networks exhibit a single-phase structure with modulus and T-g dependent on the concentration of elastically active network chains (EANC) per unit volume calculated by considering hard crosslink clusters. The rigidity of the clusters comes from small diisocyanate and trimethylolpropane units connected by urethane bonds. They are embedded in a continuous soft phase of macrodiol urethane. Physical equivalence between several kinds of network models has been demonstrated for full conversion of isocyanate-alcohol reaction. PUA networks exhibit thermodynamically one-phase structures that become a two-phase structure for high molar mass of macrodiol when the molar fraction of isocyanate groups increases. For those networks, the calculated modulus considering clusters based on polyacrylate chains seems to be a good way to approach the experimental value of the equilibrium modulus. For the same molar ratio of OH to NCO groups the range of dynamic moduli is larger for PUA than for PU. This difference can be explained by a different concentration of crosslinks in the networks.
Keywords:UNSATURATED POLYESTER RESINS;POLYMER NETWORKS;ELASTIC-MODULUS;CROSS-LINKING;MODEL;COPOLYMERIZATION;BEHAVIOR;CHAIN