Hyperbranched Poly(ester-enamine) from Spontaneous Amino-yne Click Reaction for Stabilization of Gold Nanoparticle Catalysts

Hyperbranched polymers have garnered much attention due to attractive properties and wide applications, such as drug-controlled release, stimuli-responsive nano-objects, photosensitive materials and catalysts. Herein, two types of novel hyperbranched poly(ester-enamine) (hb-PEEa) were designed and synthesized via the spontaneous amino-yne click reaction of A₂ monomer (1, 3-bis(4-piperidyl)-propane (A_2a) or piperazine (A_2b)) and B₃ monomer (trimethylolpropanetripropiolate). According to Flory's hypothesis, gelation is an intrinsic problem in an ideal A₂+B₃ polymerization system. By controlling the polymerization conditions, such as monomer concentration, molar ratio and rate of addition, a non-ideal A₂+B₃ polymerization system can be established to avoid gelation and to synthesize soluble hb-PEEa. Due to abundant unreacted alkynyl groups in periphery, the hb-PEEa can be further functionalized by different amino compounds or their derivates. The as-prepared amphiphilic PEG-hb-PEEa copolymer can readily self-assemble into micelles in water, which can be used as surfactant to stabilize Au nanoparticles (AuNPs) during reduction of NaBH₄ in aqueous solution. As a demonstration, the as-prepared PEG-hb-PEEa-supported AuNPs demonstrate good dispersion in water, solvent stability and remarkable catalytic activity for reduction of nitrobenzene compounds.