Dipartimento di Chimica - CEMIN, via Elce di Sotto 8, 06123 - Perugia, Italy.
Inorg Chem. 2010 Apr 5;49(7):3329-36. doi: 10.1021/ic902330n.
Organically modified alpha-layered zirconium phosphate samples (ZrP(C(12))(x)) containing dodecyl groups bonded to the alpha-layers through P-O-C bonds have been prepared by reaction of 1,2-epoxydodecane solutions in tetrahydrofuran (THF) with gels of partially exfoliated zirconium phosphate in THF. Two dimensional correlation solid state NMR experiments for (1)H-(13)C and (1)H-(31)P nuclei have been used to prove the formation of P-O-C bonds arising from nucleophilic attack of POH mainly to carbon 1 and, to a lesser extent, to carbon 2 of epoxydodecane. ZrP(C(12))(x) samples with x in the range from approximately 0.5 to approximately 2.0 are thermally stable up to at least 200 degrees C, and their interlayer distance increases continuously with x from approximately 20 to approximately 35 A. On the basis of structural considerations, it has been suggested that samples with low x values could intercalate aliphatic polymers. Accordingly, preliminary results have shown that molten polyethylene is intercalated in ZrP(C(12))(0.49) and ZrP(C(12))(0.73). These materials can therefore be regarded as filler candidates for polymer matrixes.
有机改性的α-层状磷酸锆样品(ZrP(C(12))(x)) 含有通过 P-O-C 键键合到α-层上的十二烷基,通过 1,2-环氧十二烷在四氢呋喃 (THF) 中的溶液与 THF 中的部分剥离的磷酸锆凝胶反应制备。二维相关固态 NMR 实验用于 (1)H-(13)C 和 (1)H-(31)P 核,以证明 P-O-C 键的形成,这主要是由于 POH 的亲核攻击,主要攻击环氧十二烷的碳 1,其次是碳 2。x 值在大约 0.5 到大约 2.0 范围内的 ZrP(C(12))(x) 样品在至少 200°C 下热稳定,其层间距连续随 x 从大约 20 到大约 35 Å 增加。基于结构考虑,有人提出低 x 值的样品可以插层进入脂肪族聚合物。因此,初步结果表明熔融聚乙烯插层进入 ZrP(C(12))(0.49) 和 ZrP(C(12))(0.73)。因此,这些材料可以被视为聚合物基质的填充剂候选物。