Abstract
We have synthesized polylactide (PLA) polymers containing five distinct lengths of fluorinated end-groups (from C3F7 to C13F27). The influence of fluorinated end-group lengths and their dynamics in chlorinated solvents (chloroform and dichloromethane) was investigated as a function of the presence of perfluorohexane (PFH) and related to the morphology of capsules of PFH obtained using these fluorinated polylactides. 19F spin–spin relaxation time (T2) measurements revealed a reduced mobility of the fluorinated units with dependency on fluorinated chain length in the order C3F7 > C8F17 > C13F27. The presence of PFH led to a further decrease on the segmental mobility, indicating the existence of fluorous interactions. The T2 relaxation time of the CF3 resonance of PLA-C3F7 decreased from 540 ± 50 ms in CDCl3 to 81 ± 15 ms after the addition of PFH. Because of these fluorous interactions, PLA polymers containing short fluorinated groups (C3F7 and C6F13) led to microcapsules with core–shell morphologies, whereas those formulated with long F units (C8F17, C11F23, and C13F27) favored the formation of multinucleated capsules as observed by confocal microscopy.
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