高分子材料与工程英文资料1.docVIP

A. Nano Materials Chapter 1 LANTHANIDE(III) OXIDE NANOCOMPOSITES WITH HEXAFLUOROISOPROPYLIDINE-BASED POLYIMIDES D. Scott Thompson 1*, D. W. Thompson1, and Robin E. Southward2* 1College of William and Mary, Department of Chemistry, Williamsburg, VA 23197; 2Structures and Materials Competency, NASA Langley Research Center, Hampton, VA 23681. *Corresponding authors. 1. INTRODUCTION 1.1 Hexafluoroisopropylidene-containing polyimides In the mid-1960’s Coe (1) and Rogers (2) developed the synthetic route to 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) for use in the preparation ofhexafluoroisopropylidene-containing aromatic polyimides. Rogers (2,3) reported the synthesis of 6FDA-based polyimides with diamines including 2,2-bis(4-aminophenyl)hexafluoropropane (4,4′-6F), 4,4′-oxydianiline (ODA), and l,3-bis(4-aminophen-oxy)benzene (1,3(4)-APB). Early interest in 6F-containing polyimides appears to have centered on the fact that the flexible, non-polarizable, and spatially bulky isopropylidene group lowers the effective symmetry of the dianhydride unit due to the availability of many low energy conformations, lowers the polarizability of chain segments, 3 4 THOMPSON et al. and increases steric constraints between chains. Such properties inhibit non- covalent intermolecular interactions, chain ordering, and crystallinity, and thus yield melt-fusible high-performance polyimides with good solubility and toughness while maintaining the thermal-oxidative stability of traditional aromatic polyimides. It was also noted (2) early that 6FDA-based polyimides were less colored than traditional polyimides such as Kapton (pyromelletic dianhydride - PMDA/ODA). Extending work with 6F-containing monomers, Jones et al. (4-7) in 1975 synthesized 2,2-bis[4-(4-aminophenoxy)- phenyl]hexafluoropropane(4-BDAF) and prepared polyimides of this diamine, including 6FDA/4-BDAF. Fluorinated aromatic polyimides with flexible 6F segments have been described by Sa