Formation of Well-Defined Vesicles by Styrene Addition to a Nonionic Surfactant and Their Polymerization Leading to Viscous Hybrid Systems

Self-assembled structures in aqueous solutions can be fixed by polymerization after adding hydrophobic monomers and can thereby be used as templates which allow to substantially alter the properties of these systems. In this work, we started from a self-assembled micellar system consisting of the nonionic surfactants tetradecyldimethylamine oxid and Pluronic L35 to which styrene was added as a polymerizable monomer. Interestingly, it was observed that styrene induces a transition from micelles to well-defined vesicles in a similar manner as a typical cosurfactant. The structural transition of the aggregates upon styrene addition as well as the structures formed after initiating a polymerization reaction were investigated by means of turbidity, dynamic and static light scattering, small-angle neutron scattering, and rheology measurements. Especially the scattering results confirmed the interesting effect of styrene on the mesoscopic structure and showed a structural evolution from rod-like micelles for low styrene concentrations to vesicles at intermediate styrene amounts, and then finally the formation of microemulsion droplets for high styrene content. Their polymerization of the vesicles again leads to a shape change to wormlike, polymerized aggregates, whose presence then results in rather viscous systems. In contrast, the microemulsions with higher styrene content then are templated and retain their size after polymerization, thereby leading to nanolattices

Monitoring the Internal Structure of Poly(<i>N</i>‑vinylcaprolactam) Microgels with Variable Cross-Link Concentration

The combination of a set of complementary techniques allows us to construct an unprecedented and comprehensive picture of the internal structure, temperature dependent swelling behavior, and the dependence of these properties on the cross-linker concentration of microgel particles based on <i>N</i>-vinylcaprolactam (VCL). The microgels were synthesized by precipitation polymerization using different amounts of cross-linking agent. Characterization was performed by small-angle neutron scattering (SANS) using two complementary neutron instruments to cover a uniquely broad Q-range with one probe. Additionally we used dynamic light scattering (DLS), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). Previously obtained nuclear magnetic resonance spectroscopy (NMR) results on the same PVCL particles are utilized to round the picture off. Our study shows that both the particle radius and the cross-link density and therefore also the stiffness of the microgels rises with increasing cross-linker content. Hence, more cross-linker reduces the swelling capability distinctly. These findings are supported by SANS and AFM measurements. Independent DLS experiments also found the increase in particle size but suggest an unchanged cross-link density. The reason for the apparent contradiction is the indirect extraction of the parameters via a model in the evaluation of DLS measurements. The more direct approach in AFM by evaluating the cross section profiles of observed microgel particles gives evidence of significantly softer and more deformable particles at lower cross-linker concentrations and therefore verifies the change in cross-link density. DSC data indicate a minor but unexpected shift of the volume phase transition temperature (VPTT) to higher temperatures and exposes a more heterogeneous internal structure of the microgels with increasing cross-link density. Moreover, a change in the total energy transfer during the VPT gives evidence that the strength of hydrogen bonds is significantly affected by the cross-link density. A strong and reproducible deviation of the material density of the cross-linked microgel polymer chains toward a higher value compared to the respective linear chains has yet to be explained