OALib Journal期刊
酸性条件下硅醇盐Si(OCH3)4水解与聚合机理的密度泛函研究
DOI: 10.3724/SP.J.1105.2013.12141
Keywords: 硅醇盐 ,水解 ,聚合 ,密度泛函理论
Abstract:
用密度泛函方法在B3LYP/6-31G(d,p)基组水平上对反应系统中的所有物种进行全优化,用CPCM溶剂模型在同一基组水平上进行了单点计算,系统研究了硅醇盐前驱体Si(OCH3)4在酸性条件下的水解、聚合机理,阐明了二者的相互竞争关系.研究发现,H2O以氢键或配位键与前驱体结合,然后通过氢转移完成水解;水分子从质子化烷氧基的对面键合并发生水解;第4级水解是H2O从对位驱逐质子化烷氧基,但不能水解完全;水解产物通过"环状模式",由氢键结合成多元环,然后发生氢转移并完成聚合;水解过程的能垒明显低于聚合过程;H+阻止水解产物聚合成环;硅正离子可引发无垒聚合反应,但在能量上并不可行.
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