原子转移自由基聚合(ATRP)和点击化学的结合为功能性聚合物的受控合成创造了前所未有的机会。含叠氮基甲基丙烯酸酯单体(例如甲基丙烯酸2-(2-(2-叠氮基乙氧基)乙氧基)乙酯,AzTEGMA),然而,在通常采用的50°C的温度下进行了较差的控制,导致显著的副反应。通过降低反应温度和单体浓度,在合理的时间范围内制备具有显著降低的多分散性的明确定义的pAzTEGMA。通过Cu(I)催化的叠氮化物-炔环加成(CuAAC)点击化学对pAzTEGMA的侧链进行后续官能化后,得到具有窄多分散性(PDI<1.30)的数均分子量(Mn)高达22kDa的官能聚合物。应用优化的聚合条件,我们还通过表面引发的ATRP(SI-ATRP)从Ti6Al4基材上接枝pAzTEGMA刷,并通过CuAAC用疏水和亲水炔有效地官能化叠氮化物封端的侧链。具有叠氮基的甲基丙烯酸酯的良好控制的ATRP和随后经由CuAAC的聚甲基丙烯酸酯的侧链的容易的高密度官能化为工程官能聚合物或表面用于各种应用提供了有用的工具。
The combination of atom transfer radical polymerization (ATRP) and click chemistry has created unprecedented opportunities for controlled syntheses of functional polymers. ATRP of azido-bearing methacrylate monomers (e.g. 2-(2-(2-azidoethyoxy)ethoxy)ethyl methacrylate, AzTEGMA), however, proceeded with poor control at commonly adopted temperature of 50 °C, resulting in significant side reactions. By lowering reaction temperature and monomer concentrations, well-defined pAzTEGMA with significantly reduced polydispersity were prepared within a reasonable timeframe. Upon subsequent functionalization of the side chains of pAzTEGMA via Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click chemistry, functional polymers with number-average molecular weights (Mn) up to 22 kDa with narrow polydispersity (PDI < 1.30) were obtained. Applying the optimized polymerization condition, we also grafted pAzTEGMA brushes from Ti6Al4 substrates by surface-initiated ATRP (SI-ATRP), and effectively functionalized the azide-terminated side chains with hydrophobic and hydrophilic alkynes by CuAAC. The well-controlled ATRP of azido-bearing methacrylates and subsequent facile high-density functionalization of the side chains of the polymethacrylates via CuAAC offers a useful tool for engineering functional polymers or surfaces for diverse applications.