Rivas M Verónica, Petroselli Gabriela, Erra-Balsells Rosa, Varela Oscar, Kolender Adriana A
Universidad de Buenos Aires, Facultad Ciencias Exactas y Naturales, Departamento de Química Orgánica, Ciudad Universitaria Pab. 2 C1428EHA Buenos Aires Argentina.
Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET)-UBA Centro de Investigación en Hidratos de Carbono (CIHIDECAR) Argentina
RSC Adv. 2019 Mar 28;9(17):9860-9869. doi: 10.1039/c9ra00398c. eCollection 2019 Mar 22.
α-Azide-ω-alkynyl ester monomers were designed and synthesized in order to obtain hydrolytically degradable polymers. The monomers were prepared from d-galactose, as a renewable resource. Environmentally benign azido-alkyne cycloaddition polymerizations were conducted to afford poly(ester-triazole)s, with complete atom economy. Although polymer formation prevailed under optimized polymerization conditions, variable proportions of cyclic oligomer byproducts were detected. The Cu-catalyzed click polymerization led regioselectively to 1,4-disubstituted triazole linkages, while the thermal, metal-free polymerization produced a random distribution of 1,4- and 1,5-disubstituted triazoles in the polymer backbone. The poly(ester-triazole)s exhibited high molecular weights ( in the range 35-85 kDa). They were soluble in organic solvents but highly insoluble in water, thus removal of the Cu(i) catalyst was simplified. The polymers were stable up to 300 °C, and had values in the range 90-100 °C. The materials were hydrolysed under either basic or strong acid conditions, and the degradation products have been characterized.
设计并合成了α-叠氮基-ω-炔基酯单体，以获得可水解降解的聚合物。这些单体由可再生资源d-半乳糖制备而成。进行了环境友好的叠氮基-炔烃环加成聚合反应，以实现完全原子经济性地制备聚（酯-三唑）。尽管在优化的聚合条件下聚合物的形成占主导，但仍检测到了不同比例的环状低聚物副产物。铜催化的点击聚合反应区域选择性地生成1,4-二取代的三唑键，而热引发的无金属聚合反应则在聚合物主链中产生1,4-和1,5-二取代三唑的随机分布。聚（酯-三唑）表现出高分子量（范围为35-85 kDa）。它们可溶于有机溶剂，但极难溶于水，因此简化了铜（I）催化剂的去除过程。这些聚合物在高达300°C时稳定，玻璃化转变温度在90-100°C范围内。这些材料在碱性或强酸条件下会发生水解，并且已对降解产物进行了表征。
