Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5209864 | Reactive and Functional Polymers | 2014 | 12 Pages |
Abstract
A series of low polydispersity cyclic PCL samples (C-PCLs), as well as their linear analogs (L-PCLs), were synthesized by click chemistry in a number average molecular weight (Mn) range of 2-22Â kg/mol. They were investigated by Polarized Light Optical Microscopy (PLOM) and Differential Scanning Calorimetry (DSC). The nucleation and overall crystallization kinetics were studied, as well as their self-nucleation behavior and SSA (Successive Self-nucleation and Annealing) thermal fractionation. Cyclic PCLs were found to nucleate and crystallize faster than linear PCLs due to: (a) faster diffusion of C-PCL chains and (b) larger supercoolings of C-PCLs at any given crystallization temperature, as compared to L-PCLs. A bell shape curve was obtained when the overall crystallization rate was examined as a function of Mn, this effect is probably due to a competition between nucleation and diffusion. It was found for the first time, that since cyclic molecules have lower entanglement densities, they can quickly recover their pseudo-equilibrium compact coil conformations upon melting and therefore exhibit much smaller crystalline memory effects than their linear counterparts of identical chain lengths. SSA revealed that C-PCLs are more sensitive to annealing than L-PCLs because their ring topology and limited lamellar chain folding facilitates crystal thickening.
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Authors
R.A. Pérez, M.E. Córdova, J.V. López, J.N. Hoskins, B. Zhang, S.M. Grayson, A.J. Müller,