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

Influence of E-glass fiber content on thermal properties of glass-fiber reinforced composites

Versatile applications of glass-fiber reinforced composites are still growing despite the fact that they have been is use for several decades. They exhibit good mechanical performances along with low densities and these are some of the advantages due to which they replaced metals in the past years, especially in transportation and electro industry. Properties of composites are dependent on the individual phases, i.e. the polymer-matrix, type of reinforcement and mineral filler, and can be tailored by properly selecting the individual constituents and their ratio. Polymer resin based on unsaturated polyesters, glass fibers and CaCO3 mineral filler is the most commonly employed in Bulk Molding Compounds (BMC), i.e. in a pre-prepared mixture of aforementioned constituents. The most common processing methods for BMCs are compression or injection molding, especially used for the mass production of small, complex-shaped components [1,2]. Since such materials are exposed to thermal stresses during processing as well as during service conditions, it is of great importance to study their thermal stability and thermal behaviour and properties. Different samples of BMCs were commercially fabricated with varying E-glass fiber and CaCO3 mineral filler contents, but keeping the content of polymer resin constant. The aim of this study was to investigate the effect of E-glass fiber weight content on physical properties and thermal behaviour of composites by means of the thermal analysis techniques. [1] R. Burns, Polyester molding compounds. New York: M. Dekker (1982). [2] JF. Monk, Thermosetting Plastics: Moulding materials and Processes. Harlow: Longman (1997)

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