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

Abstract

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–alkynecycloaddition (CuAAC). The precursor polymers were characterized viasize exclusion chromatography (SEC) and ¹H 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 via¹H NMR at ambient temperature in deuterated methylene chloride (CD₂Cl₂) solution.