Pérez Yolanda, del Hierro Isabel, Zazo Lydia, Fernández-Galán Rafael, Fajardo Mariano
Departamento Biología y Geología, Física y Química Inorgánica (E.S.C.E.T.), Universidad Rey Juan Carlos, 28933 Móstoles, Madrid, Spain.
Dalton Trans. 2015 Mar 7;44(9):4088-101. doi: 10.1039/c4dt03385j.
A family of heterogeneous catalysts has been prepared by employing different strategies: firstly by direct reaction or grafting of titanium, zinc, aluminium and magnesium precursors with dehydrated SBA-15 and secondly by reaction of the metallic derivatives with a hybrid SBA-15 mesoporous material, which possesses a new covalently bonded linker based on an amino alcohol chelate ligand. These materials have been characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), N2 adsorption-desorption, FT-IR and multi-nuclear NMR spectroscopy. The catalytic performance of the prepared materials has been studied in the ring opening polymerization of ε-caprolactone and compared with that of their homogeneous counterparts. Conversion values obtained by using homogeneous and heterogeneous catalysts depend on the metal precursor and the synthetic procedure. The most active heterogeneous Ti-SBA-15, Zn-SBA-15 and Zn-PADO-HMDS-SBA-15 catalysts produced poly(ε-caprolactone) with a narrow molecular weight distribution, close to one. In all cases polymerization was confirmed to proceed via a coordination insertion mechanism after end group analysis by (1)H NMR.
首先是通过钛、锌、铝和镁的前驱体与脱水的SBA - 15直接反应或接枝,其次是通过金属衍生物与一种杂化SBA - 15介孔材料反应,该材料具有基于氨基醇螯合配体的新型共价键连接体。这些材料通过X射线衍射(XRD)、X射线荧光(XRF)、N₂吸附 - 脱附、傅里叶变换红外光谱(FT - IR)和多核核磁共振光谱进行了表征。研究了所制备材料在ε - 己内酯开环聚合反应中的催化性能,并与它们的均相对应物进行了比较。使用均相和多相催化剂获得的转化率值取决于金属前驱体和合成方法。活性最高的多相Ti - SBA - 15、Zn - SBA - 15和Zn - PADO - HMDS - SBA - 15催化剂制备的聚(ε - 己内酯)具有窄分子量分布,接近1。在所有情况下,通过¹H NMR进行端基分析后证实聚合反应是通过配位插入机理进行的。