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Here we report the synthesis of thermosetting resins from low molar mass Kraft lignin fractions of high functionality, refined by solvent extraction. Such fractions were fully characterized by 31P NMR, 2D-HSQC NMR, SEC, and DSC in order to obtain a detailed description of the structures. Reactive oxirane moieties were introduced on the lignin backbone under mild reaction conditions and quantified by simple 1H NMR analysis. The modified fractions were chemically cross-linked with a flexible polyether diamine (Mn ≈ 2000), in order to obtain epoxy thermosets. Epoxies from different lignin fractions, studied by DSC, DMA, tensile tests, and SEM, demonstrated substantial differences in terms of thermo-mechanical properties. For the first time, strong relationships between lignin structures and epoxy properties could be demonstrated. The suggested approach provides unprecedented possibilities to tune network structure and properties of thermosets based on real lignin fractions, rather than model compounds. [ABSTRACT FROM AUTHOR]

Highlights: [•] Stereoisomers of PLLA and PDLA grafted directly at clay surface via metal-free ROP. [•] These nanohybrids were melt-processed with commercial PLA to obtain nanocomposite. [•] Grafting from approach enables to design full stereocomplex by solvent-free melting. [•] Grafting from and stereocomplexation improve rigidity and thermal properties of PLA. [•] Nanocomposites obtained show a significant improvement in oxygen-barrier properties. [ABSTRACT FROM AUTHOR]

We evaluated the combination of leaching techniques and melt blending of polymers and particles for the preparation of highly interconnected three-dimensional polymeric porous scaffolds for in vitro studies of human hepatocarcinoma processes. More specifically, sodium chloride and poly(ethylene glycol) (PEG) were used as water-soluble porogens to form porous and solvent-free poly(L,D-lactide) (PLA)-based scaffolds. Several characterization techniques, including porosimetry, image analysis and thermogravimetry, were combined to improve the reliability of measurements and mapping of the size, distribution and microarchitecture of pores. We also investigated the effect of processing, in PLA-based blends, on the simultaneous bulk/surface modifications and pore architectures in the scaffolds, and assessed the effects on human hepatocarcinoma viability and cell adhesion. The influence of PEG molecular weight on the scaffold morphology and cell viability and adhesion were also investigated. Morphological studies indicated that it was possible to obtain scaffolds with well-interconnected pores of assorted sizes. The analysis confirmed that SK-Hep1 cells adhered well to the polymeric support and emitted surface protrusions necessary to grow and differentiate three-dimensional systems. PEGs with higher molecular weight showed the best results in terms of cell adhesion and viability. [ABSTRACT FROM AUTHOR]

Employing the hydroxyl groups on the surface of Cloisite® 30B montmorillonite (Cl30B), the ring-opening polymerization of l-lactide was performed with a metal-free catalyst to yield a PLLA-g-Cl30B nanohybrid with low Mn grafted PLLA chains (i.e., 9 kg mol−1). This nanohybrid was then melt mixed with PLA 4032D from NatureWorks, which is a slow-crystallizing PLA as it contains 2% d-isomers and has a high Mn value (i.e., 123 kg mol−1). The samples were characterized by TEM, WAXS, SAXS, DSC and Polarized Light Optical Microscopy (PLOM) in order to study their crystallization kinetics in depth. The dispersion of the nanoclay was excellent and much better in the PLA/PLLA-g-Cl30B nanocomposites in comparison to PLA/Cl30B blends prepared as reference. In order to ascertain the role of the nanoclay, analogue PLA/PLLA blends without Cl30B were also prepared. The spherulitic crystallization kinetics from the melt was determined for all samples. The growth rate of neat PLA was accelerated approximately 3 times by incorporating the PLLA-g-Cl30B nanohybrid with an inorganic content of 5%. The overall crystallization kinetics from the glassy state of PLA was also accelerated in a similar way by the nanohybrid addition. Nevertheless, the PLA/PLLA blends crystallized even faster indicating that the dominant effect that causes the acceleration of the crystallization of PLA is the plasticization of PLA by the low Mn PLLA molecules. The changes in Tg of PLA also support this explanation. In the case of the PLA/PLLA-g-Cl30B nanocomposites, even though the plasticizing effect of the PLLA chains still dominates, their action is counterbalanced by their tethering on one end, as they are grafted to the surface of the exfoliated clay nanoplatelets. [ABSTRACT FROM AUTHOR]