Boosting PLA melt strength by controlling the chirality of co-monomer incorporation.

Bio-based and degradable polymers such as poly(lactic acid) (PLA) have become prominent. In spite of encouraging features, PLA has a low melt strength and melt elasticity, resulting in processing and application limitations that diminish its substitution potential vis-a-vis classic plastics. Here, we demonstrate a large increase in zero shear viscosity, melt elasticity, elongational viscosity and melt strength by random co-polymerization of lactide with small amounts, viz. 0.4-10 mol%, of diethylglycolide of opposite chiral nature. These enantiomerically pure monomers can be synthesized using one-step zeolite catalysis. Screening of the ester linkages in the final PLA chains by the ethyl side groups is suggested to create an expanding effect on the polymer coils in molten state by weakening of chain-chain interactions. This effect is suspected to increase the radius of gyration, enabling more chain entanglements and consequently increasing the melt strength. A stronger melt could enable access to more cost-competitive and sustainable PLA-based biomaterials with a broader application window. Amongst others, blow molding of bottles, film blowing, fiber spinning and foaming could be facilitated by PLA materials exhibiting a higher melt strength.

Highly efficient hyperbranched CNT surfactants: influence of molar mass and functionalization.

End-group-functionalized hyperbranched polymers were synthesized to act as a carbon nanotube (CNT) surfactant in aqueous solutions. Variation of the percentage of triphenylmethyl (trityl) functionalization and of the molar mass of the hyperbranched polyglycerol (PG) core resulted in the highest measured surfactant efficiency for a 5000 g/mol PG with 5.6% of the available hydroxyl end-groups replaced by trityl functions, as shown by UV-vis measurements. Semiempirical model calculations suggest an even higher efficiency for PG5000 with 2.5% functionalization and maximal molecule specific efficiency in general at low degrees of functionalization. Addition of trityl groups increases the surfactant-nanotube interactions in comparison to unfunctionalized PG because of π-π stacking interactions. However, at higher functionalization degrees mutual interactions between trityl groups come into play, decreasing the surfactant efficiency, while lack of water solubility becomes an issue at very high functionalization degrees. Low molar mass surfactants are less efficient compared to higher molar mass species most likely because the higher bulkiness of the latter allows for a better CNT separation and stabilization. The most efficient surfactant studied allowed dispersing 2.85 mg of CNT in 20 mL with as little as 1 mg of surfactant. These dispersions, remaining stable for at least 2 months, were mainly composed of individual CNTs as revealed by electron microscopy.