Frontal polymerisation of acrylic acid tuned by micellar aggregates in a deep eutectic solvent

Abstract

A frontal polymerisation (FP) is obtained when a polymerisation creates a spatial front of the reaction. Because of the heat of the reaction associated, a temperature spatial front is also observed. In this paper, the usual chain polymerisation of acrylic acid (AA) is studied when the monomer forms a deep eutectic solvent (DES), i.e. a liquid similar to an ionic liquid. In this DES, AA behaves as a hydrogen donor and ethylammonium chloride as a hydrogen acceptor. The use of a DES is convenient as an effective polymerisation media because the heat of the reaction can be controlled. We study the rate and the heat of polymerisation during the formation of a front using micellar structures where a bifunctional peroxide hydrophobic initiator, abbreviated Luperox, dissolves successfully. Our experiments follow the FP using infrared images and rheology. We found that micellar aggregates of different sizes are interesting modulators of the polymerisation rate and heat of the reaction. Our results show that smaller aggregates produce higher rates of reaction with a decoupled increment of temperature; in contrast to what is observed with bigger aggregates: a slow reaction rate with a coupled moderate heat of reaction.