Lastingly Colored Polylactide Synthesized by Dye-Initiated Polymerization

Abstract

An efficient synthesis strategy of a well-defined polylactide–dye conjugate in a controlled fashion is presented. The introduction of coloring species as end groups of polylactide (PLA) has been performed by using new homoleptic aminophenolate magnesium or zinc coordination compounds. The molecular structure of metal complexes has been determined in solution by NMR spectroscopy, and in the solid state by X-ray analysis. Lastingly colored polymers were obtained with 2-[4-(Nitrophenylazo)-N-ethylphenylamino]ethanol (Disperse Red 1) and 2-[4-(2-Chloro-4-nitrophenylazo)-N-ethylphenylamino]ethanol (Disperse Red 13) at very high lactide conversions, based on MALDI-ToF measurement, and the macromolecules were nearly fully chain end dye-functionalized. Based on 1H NMR, the DPn of conjugates was in the range of 10–300, which was consistent with the reaction setup. Various methods of gel-permeation chromatography (GPC) analysis were applied, and they demonstrated that the number-average molar mass (Mn) values (polystyrene (PS) standards) were a bit higher than calculated, the molar mass distribution index (ƉM) values were moderate to high, the TDA (triple detection array) system was inappropriate for analysis, measurements with PDA (photo diode array) detection at 470 nm gave nearly the same molar mass distributions such as the refractometer, and the relative absorbance of conjugates at 470 nm increased linearly versus (DPn)−1. The presented approach connects the gap between the current strategy of obtaining colored polymer fibers and the design of tailor-made initiators with eco polyesters designed for the targeted applications.

Keywords

• polylactide
• ring-opening polymerization
• zinc
• magnesium
• polymer–dye conjugate