Michael addition in reactive extrusion: A facile sustainable route to developing phosphorus based flame retardant materials

This study addresses three very important aspects of sustainable development of new flame re-tardant material, i.e. in situ solvent free synthesis of flame retardant macromolecules during thermal processing of polymers, their leaching behavior from the polymer matrix and their preliminary toxicity assessment. Polyamide 6 (PA6) was functionalized by a novel reactive extrusion process. In situ synthesis of phosphine oxide based macromolecules was obtained via Michael addition reaction of divinyl phenyl phosphine oxide (DVPPO) and piperazine during the reactive extrusion process. The formation of phosphine oxide macromolecules (oligomers and low molecular weight polymers) were confirmed by NMR study of the modified PA6 polymer and UPLC-MS analysis of extracts from PA6 samples. Elemental analysis of the modified PA6 after the extraction with chloroform and water confirmed retention of majority of phosphorus species, confirming the beneficial effect of large macromolecular additives. This non-leaching behavior of modified PA6 is an important requirement for thin walled substrates like fibers and films where long-term durability is very important. The reactive extruded PA6 was successfully processed into textile fibers via melt spinning process in a laboratory spinning plant. The presence of phosphine oxide macromolecules in PA6 matrix had a lubricating effect, which has influence in the thermal processing and final properties of the fiber. The modified PA6 was evaluated for fire performance in small-scale fire tests where it showed improved fire performance. Moreover, the preliminary toxicity assessment of the relatively unknown DVPPO, via a well-established in vitro platform showed no adverse effects on cell viability.