Influence of End Groups on the Stimulus-Responsive Behavior of Poly[oligo(ethylene glycol) methacrylate] in Water

The influence of the chemical structure of both end groups onto the lower critical solution temperature (LCST) of poly[oligo(ethylene glycol) monomethyl ether methacrylate] (POEGMA) in water was systematically investigated. POEGMA of M-n = 3550 g/mol and M-w/M-n = 1.14 prepared by reversible addition fragmentation chain transfer (RAFT) polymerization was equipped with two different functional end groups in a one-step postpolymerization reaction combining activated esters, functional amines, and functional methane thiosullonates. As end groups, n-propyl, n-hexadecyl, di(n-octadecyl), poly(ethylene glycol)-550 (PEG), 1H, 1H-perfluorononyl, azobenzene, and trimethylethylammonium groups were systematically combined with methyl, n-hexadecyl, and 1H, 1H, 2H, 2H-perfluorooctyl groups. Polymers were characterized by gel permeation chromatography, dynamic light scattering, and turbidimetry. Hydrophobic end groups at either end of the polymer chain decreased the LCST. For hydrophobic groups at both ends of the chain their influence was additive. Two large hydrophobic end groups allowed micelle formation below the LCST and an LCST higher than to be expected from nonaggregated polymers. The strongest hydrophobic effect was found for rigid aromatic end groups, which was attributed to their incompatibility with the flexible polymer chain. Charged end groups increased the LCST and could compensate for the effect of hydrophobic end groups at the opposite end group. PEG end groups could mask a hydrophobic influence of the opposite end group and stabilized the LCST.