Adsorbed and spread films of amphiphilic triblock copolymers based on poly(2,3-dihydroxypropyl methacrylate) and poly(propylene oxide) at the air-water interface

Abstract

The adsorption behavior of the novel type of water-soluble amphiphilic triblock copolymers PGMA-b-PPO-b-PGMA at the air-water interface is studied by tensiometry and monolayer techniques. In particular, (PGMA(14))(2)-PPO(34) is found to be strongly surface active (Pi(max) approximately 38.1 mN/m, cmc approximately 50 microM), in spite of having a relatively short hydrophobic PPO middle block. Time-dependent adsorption measurements exhibit two different types of adsorption kinetics depending on concentration. Monolayers deposited by spreading form pseudo-Langmuir films, in spite of (PGMA(14))(2)-PPO(34) high water solubility. The transition from a dilute to a semidilute regime during compression of the monolayer occurs at a mean molecular area around 4424 A(2)/molecule (Pi = 0.03 mN/m). Above Pi = 2.1 mN/m (1291 A(2)/molecule) PGMA segments begin to change from a flat two-dimensional conformation to loops and tails protruding into the subphase. The onset of the conformational change for PO segments takes place at a mean molecular area of approximately 625 A(2)/molecule (Pi = 15.5 mN/m). In the range Pi approximately 21.4-23.8 mN/m the PPO blocks adopt a three-dimensional conformation. A new methodology for the estimation of the amount of polymer absorbed at the interface (Gamma) as a function of the solution bulk concentration from tensiometry measurements in pseudo-Langmuir spread films is proposed. The obtained adsorption isotherm suggests the occurrence of a conformational change of the PPO block segments toward conformations having smaller molar areas for actual bulk concentrations above 6.0 x 10(-8) M. The surface tension versus polymer bulk concentration curve (gamma vs ln C) exhibits a sharp break at low concentrations, which is probably due to a conformational change within the adsorbed layer. A theoretical multiple conformation model reproduces satisfactorily the experimental dependency of surface pressure on polymer adsorption (Pi vs Gamma) at low and intermediate ranges of polymer concentrations in the solution bulk. A ratio of approximately eight between the average molecular areas at low coverage and at full coverage confirms that (PGMA(14))(2)-PPO(34) chains are highly flexible and able to adopt very different conformations during the transition of the adsorbed polymer film from a highly diluted to a nearly saturated state. There are some experimental indications that nonequilibrium effects might determine a bimodal conformational distribution within the adsorbed (PGMA(14))(2)-PPO(34) layer, which departs substantially from the equilibrium adsorption picture.