Star and miktoarm star block (co)polymers via self-assembly of ATRP generated polymer segments featuring Hamilton wedge and cyanuric acid binding motifs

Hamilton wedge (HW) end-functionalized poly(styrene) (PS-HW, M(n) = 5400 g mol(-1), PDI = 1.06), HW mid-chain functionalized poly(styrene) (PS-HW-PS, M(n) = 4600 g mol(-1), PDI = 1.04), cyanuric acid (CA) end-functionalized poly(styrene) (PS-CA, M(n) = 3700 g mol(-1), PDI = 1.04) and CA end-functionalized poly(methyl methacrylate) (PMMA-CA, M(n) = 8500 g mol(-1), PDI = 1.13) precursors were successfully synthesized via a combination of atom transfer radical polymerization (ATRP) and copper catalyzed azide-alkyne cycloaddition (CuAAC). The precursor polymers were characterized via size exclusion chromatography (SEC) and (1)H NMR with respect to both molecular weight and structure. Supramolecular homopolymer (PS-HW.PS-CA), block copolymer (PS-HW.PMMA-CA), star polymer (PS-HW-PS.PS-CA) as well as miktoarm star polymer (PS-HW-PS.PMMA-CA) were formed in solution in high yields at ambient temperature (association close to 89% for PS-HW.PS-CA, 90% for PS-HW-PS.PS-CA and 98% for PS-HW-PS.PMMA-CA) via H-bonding between the orthogonal recognition units, HW and CA. The formation of supramolecular polymers was confirmed via (1)H NMR at ambient temperature in deuterated methylene chloride (CD(2)Cl(2)) solution.