title: Use of a polyhedral oligomeric silsesquioxane (POSS)-imidazolium cation as an organic modifier for montmorillonite.
abstract: Recent studies on organically modified clays (OMCs) have reported enhanced thermal stabilities when using imidazolium-based surfactants over the typical ammonium-based surfactants. Other studies have shown that polyhedral oligomeric silsesquioxanes (POSS) also improve the thermal properties of composites containing these macromers. In an attempt to utilize the beneficial properties of both imidazolium surfactants and POSS macromers, a dual nanocomposite approach to prepare OMCs was used. In this study, the preparation of a new POSS-imidazolium surfactant and its use as an organic modifier for montmorillonite are reported. The purity, solubility, and thermal characteristics of the POSS-imidazolium chloride were evaluated. In addition, several OMCs were prepared by exchanging the Na+ with POSS imidazolium cations equivalent to 100%, 95%, 40%, 20%, and 5% of the cation exchange capacity of the clay. The subsequent OMCs were characterized using thermal analysis techniques (DSC, SDT, and TGA) as well as 29Si NMR to determine the POSS content in the clay interlayer both before and after thermal oxidation degradation. Results indicate the following: (1) the solvent choice changes the efficiency of the ion-exchange reaction of the clay; (2) self-assembled crystalline POSS domains are present in the clay interlayer; (3) the d-spacing of the exchanged clay is large (3.6 nm), accommodating a bilayer structure of the POSS-imidazolium; and (4) the prepared POSS-imidazolium exchanged clays exhibit higher thermal stabilities than any previously prepared imidazolium or ammonium exchanged montmorillonite.
authors.affiliation: Chemistry Department, U.S. Naval Academy, Annapolis, Maryland 21402, USA. dfox@american.edu
authors.forename: Douglas M
authors.initials: DM
authors.lastname: Fox
authors.forename: Paul H
authors.initials: PH
authors.lastname: Maupin
authors.forename: Richard H
authors.initials: RH
authors.lastname: Harris
authors.forename: Jeffrey W
authors.initials: JW
authors.lastname: Gilman
authors.forename: Donald V
authors.initials: DV
authors.lastname: Eldred
authors.forename: Dimi
authors.initials: D
authors.lastname: Katsoulis
authors.forename: Paul C
authors.initials: PC
authors.lastname: Trulove
authors.forename: Hugh C
authors.initials: HC
authors.lastname: De Long