Polymerisation of liquid crystalline phases in binary surfactant/water systems

The binary phase behaviour of two potentially polymerisable quaternary ammonium surfactants in water has been investigated. Allyldodecyldimethylammonium bromide (ADAB) a single-chain surfactant displays a conventional phase progression upon increasing concentration. Whereas the doublechain analogue allyldidodecylmethylammonium bromide (ADDAB) forms two lamellar liquid crystalline phases built from surfactant bilayers, which transform via a first order phase transition. The formation of two distinct lamellar phases and their coexistence has been evidenced by optical microscopy, small-angle x-ray scattering and D₂O deuterium quadrupolar nuclear magnetic resonance spectroscopy. The lamellar phase formed at higher surfactant compositions is a normal lamellar phase (typeL) consisting of bilayers which are on average parallel and flat. The lower compositional lamellar phase (typeL) in contrast may not be comprised of planar bilayers but rather aggregates having a high degree of curvature in comparison to those of theL phase. The presence of the allyl polymerisable moiety in the head group position of these surfactants has the effect of reducing the rigidity of the surfactant and increasing its solubility in comparison to nonpolymerisable analogues. Polymerisation of the surfactants was attempted by using thermal and photochemical initiation in isotropic and self-assembled systems. Polymerisation occurred to approximately 30% for DADB but did not occur for ADDAB. Where polymerisation did occur the polymer was incorporated into the monomer matrix by interweaving between the surfactant aggregates. The polymers had a molecular wieght not greater than 8000 Daltons, independent of the monomer concentration of the original solution and type of polymerisation.