国外高分子科学与工程教材与参考的资料96320.pdfVIP

Chapter 20 CONDENSATION COPOLYMERIZATION VIA Ru-CATALYZED REACTION OF o-QUINONES OR WITH OLIGODIMETHYLSILOXANES Joseph M. Mabry and William P. Weber* K. B. and D. P. Loker Hydrocarbon Research Institute Department of Chemistry, University of Southern California Los Angeles, CA 90089-1661 1. INTRODUCTION 1.1 Poly(silyl ether)s Condensation polymers are those in which the repeating unit lacks certain atoms present in the monomer(s) from which it is formed (1). By comparison, addition polymers are formed from monomers without loss of small molecules. Copolymers of poly(dimethylsiloxane) (PDMS) are of interest for a variety of applications. Copolymers, which incorporate oligodimethyl- siloxane (ODMS) units may have similar to that of PDMS, but exhibit no detectable (2). They are attractive candidates for low temperature sealants and adhesives. There is also interest in the utility of poly(silyl ether)s as elastomers (3), sensor materials (4), and polymer membranes (5). Symmetrical poly(silyl ether)s have been prepared by the condensation polymerization of dialkoxysilanes and with loss of alcohol (6-8). 1.2 Transition Metal Catalysis There is considerable interest in transition metal catalyzed polymer- izations (9,10). The instability of poly(silyl ether)s and poly(silyl enol ether)s in acidic or basic media makes transition metal catalyzed polymerization 287 288 MABRY AND WEBER under neutral conditions attractive. High molecular weight poly(silyl ether)s have been obtained by Rh or Pd-catalyzed condensation of bis(silane)s with diols (figure 1) (11-14). We have reported the Ru-catalyzed additio