Polymer chains grafted "to" and "from" layered silicate clay platelets

Polymerization of lauryl methacrylate "to" and "from" the surface of montmorillonite platelets was studied under a range of different reaction conditions. The polymerization was performed in order to achieve better organic coverage of the platelets, thus facilitating their exfoliation in the polymer matrices. For polymerization "to" the surface, a methacrylic functionality was first generated on the clay surface which was subsequently polymerized with the external lauryl methacrylate monomer. Substantial amounts of the polymer could be attached to the surface when lower polymerization temperatures and longer reaction times were used. Bulk polymerization was more effective in increasing the amount of polymer mass on the surface. In order to achieve polymerization "from" the surface, a bicationic initiator was first ionically bound on the surface followed by polymerization with lauryl methacrylate. Under the nonliving conditions, however, no significant amount of polymer could be grown from the surface. Nitroxide-mediated living polymerization was successful in eliminating suspected termination reactions leading to substantial gains in the organic mass bound to clay surfaces. Care was taken to avoid the presence of excess of unbound ammonium ions which can interfere in the grafting of polymer chains on the surface. X-ray diffraction and transmission electron microscopy in conjunction with thermogravimetric analysis confirmed the grafting of the polymer chains on the surface. (c) 2007 Elsevier Inc. All rights reserved.