A novel route to obtain highly ordered self-assembled honeycomb films has been investigated by a bottom-up process. A polymer with one chain end ionic functionality has been synthesized in a one-step reaction by nitroxide-mediated polymerization. This ionomer synthesis represents a very simple way, and honeycomb structured films have been observed after solvent evaporation in a long-range distance of few hundred microns in a very regular ordered arrangement. These films are simply prepared by spreading out polymers CS 2 solutions without additives over various substrates as well on inorganic surfaces as onto different polymeric substrates such as flexible PVC sheet or rigid PMMA plate. Different experimental parameters, such as polymer concentration or wet thickness, have been checked to tune the pores size and thus the honeycomb morphologies. An elegant technique based on reflected and transmitted light has been used to correlate the pores size inside and on the top of the film. This highly ordered hexagonal pattern on the polymeric surfaces suggests the possibility of taking advantage of the microtextures for inducing optical interferences but also to modify the color of this bioinspired material as a function of their visual angle as in nature.

Synthetic surfactants are widely used in emulsion polymerization, but it is increasingly desirable to replace them with naturally derived molecules with a reduced environmental burden. This study demonstrates the use of saponins as biodegradable and renewable surfactants for emulsion polymerization. This chemical has been extracted from soapnuts by microwave assisted extraction and characterized in terms of surfactant properties prior to emulsion polymerization. The results in terms of particle size distribution and morphology control have been compared to those obtained with classical nonionic (NP40) or anionic (SDS) industrial surfactants. Microwave-extracted saponins were able to lead to latexes as stable as standard PS latex, as shown by the CMC and CCC measurements. The saponin-stabilized PS particles have been characterized in terms of particle size and distribution by Dynamic Light Scattering and Asymmetrical Flow Field Flow Fractionation. Monomodal and monodispersed particles ranging from 250 to 480 nm in terms of diameter with a particle size distribution below 1.03 have been synthesized.

A novel methodology used to overcome the predominance of π–π interactions on the organization of rod–coil copolymer is reported in this paper. We demonstrated changes in the self-assembly morphology of poly­(3-hexylthiophene)-b-poly­(methyl methacrylate) (P3HT-b-PMMA) block copolymer BCP, by introducing an ionic group to the linking unit between the two blocks. A neutral polymer precursor was synthesized from ethynyl-terminated P3HT and azido-terminated PMMA via Huisgen’s 1,3-dipolar cycloaddition. Then two 1,2,3-triazolium-based block copolymers with different counteranions were obtained by a quaternization of 1,2,3-triazole groups with methyl iodide, and subsequent anion exchange was observed with a fluorinated salt, bis­(trifluoromethane) sulfonimide salt. Atomic force microscopy, modulated differential scanning calorimetry, and X-ray scattering were used to prove that the crystallization of the conjugated block is disrupted by the additional ionic interactions imposed to the system. The 1,2,3-triazolium-based BCP with iodide as the counterion exhibited highly organized well-defined fibrils, as the diblock phase segregation χ becomes predominant over the rod–rod interaction μ. When the more stable and larger NTf2 – was used as counterion, P3HT phase was disrupted and no crystallization was observed. This methodology could be a useful strategy to open the range of nanomorphologies reachable with a semiconducting polymer for electronic or photovoltaic applications.