Université de Lyon, INSA-Lyon, Université Claude Bernard Lyon 1, Ingénierie des Matériaux Polymères (UMR-CNRS 5223), Villeurbanne Cedex, France.
Biomacromolecules. 2010 Oct 11;11(10):2797-803. doi: 10.1021/bm100872h.
The design of dialkyne and diazide functionalized dianhydrohexitol stereoisomers (1-6) afforded a new family of starch-based polytriazoles (7-15) with defined stereochemistry through A(2) + B(2) CuAAC step growth polymerization. The present strategy gave rise to polytriazoles having a high biosourced weight fraction (superior to 60% wt) and exhibiting relatively high molar masses (M(n) = 8-17 kg/mol) that could be easily dissolved in DMF or DMSO. The obtained materials were amorphous and displayed high transition temperatures (T(g) = 125-166 °C) as well as good resistance to thermal degradation (T(d10) = 325-347 °C). Monomer stereochemistry proved to be a crucial parameter aiming at generating polymers with high T(g). Thus, optimal thermal properties were obtained with monomers having RR absolute configuration of the C-2 and C-5 carbon atoms (isomannide configuration).
通过 A(2) + B(2) CuAAC 逐步增长聚合反应，设计了二炔基和叠氮基官能化的二脱水己糖醇立体异构体（1-6），得到了一系列具有确定立体化学结构的新型淀粉基聚三唑（7-15）。该策略得到的聚三唑具有较高的生物源重量分数（超过 60%wt），且摩尔质量相对较高（M(n) = 8-17 kg/mol），可溶于 DMF 或 DMSO。所得到的材料为无定形，显示出较高的玻璃化转变温度（T(g) = 125-166°C）和良好的热稳定性（T(d10) = 325-347°C）。单体的立体化学被证明是生成具有高 T(g)的聚合物的关键参数。因此，具有 C-2 和 C-5 碳原子 RR 绝对构型（异甘露糖构型）的单体可获得最佳的热性能。
