A chain-extender based on 1,1 0 -Carbonyl-Bis-Caprolactam (CBC) was melt compounded with a commercial Polyamide 6 (PA6) by using a twin screw extruder. Rheological, thermal, and mechanical tests were performed on the resulting materials to evaluate the chain extension capability of CBC. Rheological tests on the compounded pellets and relative viscosity measurements on solubilized samples evidenced an increase of the viscosity values with the chain-extender amount, while the opposite trend was determined increasing the high temperature residence time. Terminal group analysis confirmed the increase of the molecular weight with the CBC content and highlighted a preferential reactivity of the chain-extender with aminic end groups. Differential scanning calorimetry (DSC) tests showed how both melting and relative crystallinity of the up-graded samples decreased with the CBC amount. Elastic and yield properties of chain-extended PA6 were similar to those of neat PA6 grades at different molecular weight, while crystallinity drop due to chain extension was responsible of an increase of the strain at break values. POLYM. ENG. SCI., 54:158-165, 2014. ª
A qualitative approach to analyze the electronic origin of substituent effects on the paramagnetic part of chemical shifts is described and applied to few model systems, where its potentiality can be appreciated. The formulation of this approach is based on the following grounds. The influence of different inter- or intramolecular interactions on a second-order property can be qualitatively predicted if it can be known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals that define some experimental trends of magnetic shielding constants. This approach is applied first to study the electronic origin of methyl-beta substituent effects on both (15)N and (17)O chemical shifts, and afterward it is applied to a couple of examples of long-range substituent effects originated in charge transfer interactions such as the conjugative effect in aromatic compounds and sigma-hyperconjugative interactions in saturated multicyclic compounds.
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