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Keywords:

  • copper-catalyzed azide–alkyne cycloaddition (CuAAC);
  • cyanuric acid;
  • dynamic light scattering;
  • graft Hamilton wedge;
  • hydrogen bonding;
  • modular ligation;
  • nitroxide-mediated radical polymerization (NMP);
  • self-assembly;
  • star-shaped polymer;
  • supramolecular chemistry

Abstract

A well-defined random copolymer of styrene (S) and chloromethylstyrene (CMS) featuring lateral chlorine moieties with an alkyne terminal group is prepared (P(S-co-CMS), equation image = 5500 Da, PDI = 1.13). The chloromethyl groups are converted into Hamilton wedge (HW) entities (P(S-co-HWS), equation image = 6200 Da, PDI = 1.13). The P(S-co-HWS) polymer is subsequently ligated with tetrakis(4-azidophenyl)methane to give HW-functional star-shaped macromolecules (P(S-co-HWS))4, equation image = 25 100 Da, PDI = 1.08). Supramolecular star-shaped copolymers are then prepared via self-assembly between the HW-functionalized four-arm star-shaped macromolecules (P(S-co-HW))4 and cyanuric acid (CA) end-functionalized PS (PS–CA, equation image = 3700 Da, PDI = 1.04), CA end-functionalized poly(methyl methacrylate) (PMMA–CA, equation image = 8500 Da, PDI = 1.13) and CA end-functionalized polyethylene glycol (PEG–CA, equation image = 1700 Da, PDI = 1.05). The self-assembly is monitored by 1H NMR spectroscopy and light scattering analyses.