Abstract
Mono-anthracene-terminated poly-L-lactide (A-PLLA) and mono-maleimide-terminated poly-D-lactide (M-PDLA) were prepared by ordinary lactide polymerization with initiators containing the corresponding functional groups. The resulting A-PLLA was allowed to dimerize by the reaction of its terminal hydroxyl with hexamethylene diisocyanate (HMDI) to obtain bis-anthracene-terminated PLLA (A-PLLA-A). The terminal Diels-Alder coupling between A-PLLA and M-PDLA and between A-PLLA-A and M-PDLA spontaneously gave stereo di- (d-sb-PLA) and tri-block (t-sb-PLA) copolymers, respectively, whose block sequences could be readily controlled by changing the molecular weight of the A-PLLA and M-PDLA prepolymers. The resultant d-sb-PLA and t-sb-PLA samples were found to have excellent thermal and thermo-mechanical properties due to the easy formation of stereocomplex crystals of PLLA and PDLA. These synthetic methods, which were based on polymer coupling, can be a facile route to the fabrication of stereo block polylactides possessing excellent properties.
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Acknowledgements
This work was part of a commissioned project, ‘Development of the Fundamental Technology on Green and Sustainable Chemical Processes’ that was supported by New Energy and Industrial Technology Development Organization (NEDO). Musashino Chemical Laboratory, Ltd. and Unitica Co., Ltd. are highly acknowledged for their support and helpful discussions.
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Masutani, K., Lee, C. & Kimura, Y. Synthesis and properties of stereo di- and tri-block polylactides of different block compositions by terminal Diels-Alder coupling of poly-L-lactide and poly-D-lactide prepolymers. Polym J 45, 427–435 (2013). https://doi.org/10.1038/pj.2012.161
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DOI: https://doi.org/10.1038/pj.2012.161
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