Critical Effect of Segmental Dynamics in Polybutadiene/Clay Nanocomposites Characterized by Solid State 1H NMR Spectroscopy
作者：Y. Gao, R.C. Zhang, W.F. Lv, Q.J. Liu, X.L. Wang,* P.C. Sun, H. H. Winter, G. Xue
關鍵字：Polybutadiene, NMR, Dynamics, clay
論文來源：期刊
具體來源：J. Phys. Chem. C 2014, 118, 5606?5614
發表時間：2014年
The segmental dynamics of rigid, intermediate, and mobile molecular components in carboxyl terminated polybutadiene (CTPB)/organo?clay (C18?clay) systems was characterized by fully refocused 1H NMR FID. In addition, 1H DQ NMR experiments allowed semiquantitative monitoring of changes in segmental dynamics near the interface. Both methods suggest a critical concentration of 60 wt % CTPB, indicating a saturation effect for the surface-adsorbed polymer. While the critical concentration value of a polymer/clay system can be measured in several ways, this is its first direct evidence at the molecular scale. The polymer?clay interaction is found to profoundly change with the removal of the CTPB end group or the organic modifier on the clay surface thus impacting the polymer segmental dynamics near the clay surface. In C18?clay by itself, with increasing temperature, the dynamic behavior of surface modifier changes from homogeneous to heterogeneous, on the basis of which the nonreversible exfoliation process of CTPB/clay nanocomposites could be explained at the molecular level. Based on the 1H NMR results, a tentative model was proposed to illustrate the evolution of the structure and segmental dynamics in CTPB/organo?clay nanocomposites.