Franco Roberto W A, Brasil Carlos A, Mantovani Gerson L, Azevedo Eduardo R de, Bonagamba Tito J
São Carlos Institute of Physics, University of São Paulo, P.O.Box 369, São Carlos, SP 13560-970, Brazil.
Materials (Basel). 2012 Dec 21;6(1):47-64. doi: 10.3390/ma6010047.
In this study, Cross-Polarization Magic-angle Spinning CP/MAS, 2D Exchange, Centerband-Only Detection of Exchange (CODEX), and Separated-Local-Field (SLF) NMR experiments were used to study the molecular dynamics of poly(ethylene glycol) (PEG) inside Hectorite/PEG intercalation compounds in both single- and double-layer configurations. The results revealed that the overall amplitude of the motions of the PEG chain in the single-layer configuration is considerably smaller than that observed for the double-layer intercalation compound. This result indicates that the effect of having the polymer chain interacting with both clay platelets is to produce a substantial decrease in the motional amplitudes of those chains. The presence of these dynamically restricted segments might be explained by the presence of anchoring points between the clay platelets and the PEG oxygen atoms, which was induced by the Na⁺ cations. By comparing the PEG motional amplitudes of the double-layered nanocomposites composed of polymers with different molecular weights, a decrease in the motional amplitude for the smaller PEG chain was observed, which might also be understood using the presence of anchoring points.
在本研究中,采用交叉极化魔角旋转(CP/MAS)、二维交换、仅检测交换的中心带(CODEX)和分离局部场(SLF)核磁共振实验,研究了单层和双层结构的锂皂石/聚乙二醇(PEG)插层化合物中聚乙二醇(PEG)的分子动力学。结果表明,单层结构中PEG链运动的整体幅度明显小于双层插层化合物中观察到的幅度。该结果表明,聚合物链与两个粘土片层相互作用的效果是使这些链的运动幅度大幅降低。这些动态受限链段的存在可能是由Na⁺阳离子诱导的粘土片层与PEG氧原子之间的锚定点的存在所解释的。通过比较由不同分子量聚合物组成的双层纳米复合材料的PEG运动幅度,观察到较小PEG链的运动幅度降低,这也可以用锚定点的存在来理解。