Effects of network junctions and defects on the crystallization of model poly(ethylene glycol) networks.

Polymer crystallization drastically changes the physical properties of polymeric materials. However, the crystallization in polymer networks has been little explored. This study investigated the crystallization behavior of a series of poly(ethylene glycol) (PEG) networks consisting of well-defined branched precursors. The PEG networks were prepared by drying gels synthesized at various conditions. The PEG networks showed slower crystallization with lower final crystallinity than uncrosslinked PEGs with amine end groups. Surprisingly, the effect of network formation was not as significant as that of the relatively bulky end-groups introduced in the uncrosslinked polymer. The molecular weight of the precursor PEG, or equivalently the chain length between neighboring junctions, was the primary parameter that affected the crystallization of the PEG networks. Shorter network chains led to lower crystallization rates and final crystallinity. This effect became less significant as the network chain length increased. On the other hand, the spatial and topological defects formed in the gel synthesis process did not affect the crystallization in the polymer networks at all. The crystallization in the polymer networks seems insensitive to these mesoscopic defects and can be solely controlled by the chain length between junctions.