Polybutadiene model networks —synthesis, mechanical characterization and comparison with rubber elasticity models

Abstract

Model networks of defined crosslink density are prepared via nonradical statistical crosslinking of polybutadiene in bulk and concentrated solution using a masked bistriazolinedione as crosslinker. The kinetics of crosslinking is monitored by FT-IR-spectroscopy. The reaction follows pseudo-1st-order reaction kinetics. The activation parameter of the crosslinking reaction is estimated from crosslinking at various temperatures. Networks of deuterated polybutadiene are prepared by this reaction in a wide range of crosslink densities. The stress strain behavior is analyzed according to the Junction Constraint-Theory of rubber elasticity (JCT) and to the approach introduced by Graessley accounting for trapped topological constraints. The analysis clearly demonstrates that trapped entanglements contribute to the mechanically effective cycle rank, i.e., to the modulus in this system in the small and large strain limit.