Dendritic polymers containing a dimethylsilyl linked dihydroxybenzyl alcohol backbone: divergent synthesis, aggregation, functionalization, and an evaluation of their applications in catalysis
作者:Olivier Bourrier、Ashok K. Kakkar
DOI:10.1039/b301778h
日期:——
A divergent synthetic approach to the construction of dimethylsilyl linked dihydroxybenzyl alcohol based dendrimers via acid–base hydrolytic chemistry of bis(dimethylamino)dimethylsilane with 3,5-dihydroxybenzyl alcohol, is reported. The peripheral OH groups lead to significant aggregation that was studied using FT-IR and UV-Vis spectroscopies, light scattering and transmission electron microscopy. Different generations of dendrimers could be easily functionalized at the periphery with phosphorus donor groups that were subsequently bound to RhCl(1,5-C8H12). Such organometallic dendrimers were found to be active and recoverable catalysts for hydrogenation of decene. The catalytic efficiency was found to be dependent on the number of generations and reaction time. An uncontrolled reaction of Me2Si(NMe2)2 with 3,5-dihydroxybenzyl alcohol in a multi-step addition process or one-pot reaction, led to the formation of hyperbranched polymers in which the build-up of the polymeric backbone was found to be dependent on the preferential reactivity and sterics at the benzylic center, as observed during dendrimer construction.
本文报道了一种通过酸碱水解法,利用双(二甲氨基)二甲基硅烷与3,5-二羟基苄醇反应,合成基于二甲基硅烷连接的二羟基苄醇基树枝状大分子的结果。通过FT-IR和UV-Vis光谱学、光散射和透射电子显微镜研究了外围羟基导致的重要聚集现象。不同代的树枝状大分子在外围可轻松引入磷供体基团,随后与RhCl(1,5-C8H12)结合。这些有机金属树枝状大分子被发现是用于癸烯加氢反应的活性可回收催化剂。催化效率取决于代数和反应时间。在多步加成过程或一步反应中,Me2Si(NMe2)2与3,5-二羟基苄醇的无控反应导致形成超支化聚合物,聚合物骨架的构建依赖于苄基中心的优先反应性和空间位阻,与树枝状大分子的构建过程观察到的情况一致。