Polyether-Based Diblock Terpolymer Micelles with Pendant Anthracene Units—Light-Induced Crosslinking and Limitations Regarding Reversibility

Abstract

The synthesis of 9-methylanthracenyl glycidyl ether (AnthGE) as a crosslinkable monomer that can be applied in anionic ring opening polymerization is reported. Diblock terpolymers of the composition methoxy-poly(ethylene oxide)-block-poly(2-ethylhexyl glycidyl ether-co-9-methylanthracenyl glycidyl ether) (mPEO-b-P(EHGE-co-AnthGE) with 10 to 24 wt% of AnthGE are synthesized and characterized. Their micellization behavior, as well as their light-induced core-crosslinking via irradiation with UV light (λ = 365 nm) is studied. The results are compared with studies on the dimerization, and the dimer cleavage via irradiation with UV–C light (λ = 254 nm), of the same diblock terpolymer in organic solution, and the small-molecule model compound 9-methoxymethylanthracene. Differences in 1H NMR spectra of the crosslinked or dimerized compounds and reaction kinetics of the dimerization reactions under different conditions suggest possible side reactions for the case of the core-crosslinking of micelles in aqueous solution. These side reactions limit the reversibility of the anthracene dimerization reaction in aqueous solutions, even if the anthracene molecule is encapsulated within the hydrophobic core of a polymeric micelle.