Self-assembled arrays as media for the formation of polymers and copolymers: New polysurfactants and polypyrrole

Self-assembled arrays (SAAs) of surfactants (or amphiphiles) in bulk aqueous phases or at the solid-water interface exhibit significant solubilization of many organic molecules. Therefore, SAAs, micelles in aqueous phases or admicelles (or adsorbed monolayers) at solid-water interfaces have been used as media to enhance chemical reactions, produce unique polymers, and coat thin polymer films on substrates.; As an extention of this technique, SAAs at the metal oxide-water interface and in aqueous phases were investigated as media to copolymerize non-compatible monomers (styrene and sodium 10-undecen-1-yl sulfate 1). SAAs were also studied as media to coat electronically conducting thin polymer films on metal oxide surfaces. In addition, the solubilization of organics in the polymeric micellar system and adsorbed SAAs on metal oxide surfaces were studied for potential applications in the field of separation and controlled release of organics.; An unique copolymer of styrene and monomeric surfactant 1 was successfully prepared using both adsorbed SAA of 1 on alumina and micellar 1. The content of surfactant units in the copolymer was higher with the adsorbed SAA 1 on alumina than that with the micellar 1.; Hexanoic acid was used as a substitute for surfactant to coat thin polypyrrole (PPY) films on alumina particles. Adsorption phenomena exhibited by hexanoic acid in the water-alumina system at various pH levels were investigated using adsorption isotherms and it was demonstrated that the adsorption of hexanoic acid is a strongly pH dependent, complicated process. In order to determine optimum PPY coating condition on alumina particles, adsolubilization studies of pyrrole either on or in adsorbed hexanoic acid arrays was accomplished. It was found that a pH level of 4 and 45 mM initial hexanoic acid concentration with 1 g of alumina particles and 10 mL water was the most efficient condition to coat thin PPY films on alumina. The resulting PPY coated alumina showed a higher contact conductivity {dollar}(4.7 times 10sp{lcub}-2{rcub}{dollar} S/cm) than pure PPY powders {dollar}(1.1 times 10sp{lcub}-2{rcub}{dollar} S/cm), even with a very small amount (12 Wt%) of PPY in the composite material. Further characterization of both the adsorbed hexanoic acid on mica and thin PPY films coated on mica was carried out using the Wilhelmy plate method, atomic force microscopy (AFM), scanning tunneling microscopy (STM), and reflection-adsorption IR (RAIR).; Both polymeric and copolymeric micelles have been prepared via the polymerization of 1 in the micellar phase and characterized. From the solubilization studies, it was revealed that both polymeric and copolymeric micelles from 1 were not very effective at solubilizing or binding m-chlorophenol. However, solubilization of t-butylphenol in both polymeric and copolymeric micelle of 1 is very effective. These results have been explained in analogy to the adsorption of polar organic solutes in the vicinity of the head groups of ionic micelles.; Using pH sensitive adsorbed SAA's of hexanoic acid an alumina, the surface of alumina could be controlled to be either hydrophobic or hydrophilic. By changing from pH 4 to pH 5 at an initial 250 mM concentration of hexanoic acid, it has been revealed that up to 60% of guest organic molecules can be released from their bound state. This quick pH response of the adsorbed SAA may be interesting for future applications.