Separation of Poly(styrene-block-t-butyl methacrylate) Copolymers by Various Liquid Chromatography Techniques

The separation of a mixture of three poly(styrene-block-t-butyl methacrylate) copolymers (PS-b-PtBMA), consisting of polystyrene (PS) blocks of similar length and t-butyl methacrylate (PtBMA) blocks of different lengths, was performed using various chromatographic techniques, that is, a gradient liquid chromatography on reversed-phase (C18 and C8) and normal-phase columns, a liquid chromatography under critical conditions for polystyrene as well as a fully automated two-dimensional liquid chromatography that separates block copolymers by chemical composition in the first dimension and by molar mass in the second dimension. The results show that a partial separation of the mixture of PS-b-PtBMA copolymers can be achieved only by gradient liquid chromatography on reversed-phase columns. The coelution of the two block copolymers is ascribed to a much shorter PtBMA block length, compared to the PS block, as well as a small difference in the length of the PtBMA block in two of these copolymers, which was confirmed by SEC-MALS and NMR spectroscopy

Degradation of PLA/ZnO and PHBV/ZnO composites prepared by melt processing

Composites of polylactide (PLA) or poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and ZnO nanoparticles (nZnO) were prepared by melt processing. During extrusion and moulding nano ZnO formed aggregates with sizes between 0.5 and 5 μm in PLA and between 0.5 and 15 μm in PHBV. Nano ZnO acted as a disruptor of PLA crystallization process and shifted the polymer glass transition temperature to lower temperatures. This was explained by degradation of PLA polymer chains during melt processing. SEC, FTIR and 1H NMR confirmed that PLA degradation was correlated to nZnO concentration. The effect of nZnO on crystallization of PHBV matrix was much less intense which was shown by TGA. On the other hand, PHBV showed significantly lower thermal stability than PLA. ZnO participated as a reactant and an accelerator in the degradation reaction of PLA and at a smaller extent with PHBV. The results of this study revealed that addition of pure nZnO in concentrations higher than 0.1 wt.% is not recommended for the preparation of PLA/nZnO composites by melt processing while in the case of PHBV the nZnO concentration may be higher but it should not exceed 1.0 wt.%. The exposure time of these materials to high temperatures during melt processing should also be minimized

Synthesis of Dendronized Poly(l-Glutamate) via Azide-Alkyne Click Chemistry

Poly(l-glutamate) (PGlu) was modified with a second-generation dendron to obtain the dendronized polyglutamate, P(Glu-D). Synthesized P(Glu-D) exhibited a degree of polymerization (DPn) of 46 and a 43% degree of dendronization. Perfect agreement was found between the P(Glu-D) expected structure and the results of nuclear magnetic resonance spectroscopy (NMR) and size-exclusion chromatography coupled to a multi-angle light-scattering detector (SEC-MALS) analysis. The PGlu precursor was modified by coupling with a bifunctional building block (N3-Pr-NH2) in the presence of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) coupling reagent. The second-generation polyamide dendron was prepared by a stepwise procedure involving the coupling of propargylamine to the l-lysine carboxyl group, followed by attaching the protected 2,2-bis(methylol)propionic acid (bis-MPA) building block to the l-lysine amino groups. The hydroxyl groups of the resulting second-generation dendron were quantitatively deprotected under mild acidic conditions. The deprotected dendron with an acetylene focal group was coupled to the pendant azide groups of the modified linear copolypeptide, P(Glu-N3), in a Cu(I) catalyzed azide-alkyne cycloaddition reaction to form a 1,4-disubstituted triazole. The dendronization reaction proceeded quantitatively in 48 hours in aqueous medium as confirmed by 1H NMR and Fourier transform infrared spectroscopy (FT-IR) spectroscopy