Effect of chain length distribution on thermal characteristics of model polytetrahydrofuran (PTHF) networks

A series of model polytetrahydrofuran (PTHF) networks were synthesized via end-linking reactions of α, ω-allyl PTHF oligomers with a stoichiometric tetrafunctional crosslinker. The telechelic PTHF oligomers were synthesized by living cationic ring-opening polymerization of tetrahydrofuran followed by a termination reaction with allyl alcohol. Networks thus prepared have well-controlled architecture in terms of the inter-crosslink chain length (Mc) and chain length distribution: resulting in unimodal, bimodal and clustered structures. Unimodal network was prepared by using polymer chains of same molecular weight, bimodal networks were synthesized by using two groups of polymer chains with different average molecular weights, and the clusters are prepared by incorporating clusters of networks with small molecular weight chains in a network matrix made of longer chains. Thermal characteristics of these model networks were investigated as a function of crosslink density, as well as inhomogeneities of crosslink distribution using DSC. We demonstrate that glass transition temperature (Tg) and crystallization behavior (melting temperature and crystallinity) of the networks are both strongly influenced by crosslink density (Mc). By comparing the unimodal, bimodal and clustered networks with similar average Mc, the effects of inhomogeneities in the crosslink distribution on the thermal properties were also investigated. Results show that inhomogeneities have trivial influence on Tg, but strongly affects the crystallization behavior. Moreover, the effects of the content ratio and length ratio between long and short chains, and the effects of cluster size and size distribution on the thermal characteristics were also studied.