Journal of Physical Chemistry, Vol.98, No.32, 7891-7898, 1994
Fluorescence Probe Study of Micelle Formation of Poly(Ethylene Oxide) Macromonomers in Water
Micelle formation in aqueous solutions of a series of poly(ethylene oxide) (PEG) macromonomers has been investigated by steady-state and time-resolved fluorescence techniques using pyrene as a probe. These molecules have the structure C-1-PEO-C-m-S-n, where m is the length of the alkyl chain attached to the para position of styrene and n is the degree of polymerization of PEG. The partition coefficients (K-v) of pyrene between the aqueous and micellar phases, the critical micellar concentration (cmc), and the micellar aggregation number (N-agg) are determined and compared to those of other more conventional surfactants. The PEO macromonomers were found to form micelles with a very weak hydrophobic core, K-v = 0.27 X 10(4) for C-1-PEO-C-4-S-53 and 0.52 x 10(4) for C-1-PEO-C-7-S-53. The measurements of partitioning, excimer emission, and vibrational fine structure of pyrene fluorescence (I-1/I-3) afford cmc values of 0.90-0.85 wt % for C-1-PEO-C-1-S-53, 0.76-0.71 wt % for C-1-PEO-C-4-S-53, and 0.29-0.25 wt % for C-1-PEO-C-7-S-53 solutions. N-agg is determined as 27 for C-1-PEO-C-4-S-53 and 38 for C-1-PEO-C-7-S-53 micelles. A micelle formation mechanism is proposed for nonionic polymeric surfactants with weakly hydrophobic groups.
Keywords:CROWN ETHER SURFACTANT;COPOLYMERIZATION REACTIVITY;RADICAL COPOLYMERIZATION;PHOTOCHEMICAL-REACTIONS;ORGANIZED ASSEMBLIES;FORMING MONOMERS;POLYMERIZATION;SYSTEMS;PHOTOPOLYMERIZATION;SOLUBILIZATION