Catalytic Cs2CO3 Promotes “Silyl Method”-Type Polycondensation英文文献资料.docVIP

Open Journal of Polymer Chemistry, 2012, 2, 1-5 /10.4236/ojpchem.2012.21001 Published Online February 2012 (http://www.SciRP.org/journal/ojpchem) Catalytic Cs2CO3 Promotes “Silyl Method”-Type Polycondensation Claus Vogel, Jochen Meier-Haack Leibniz-Institut für Polymerforschung Dresden e.V., Dresden, Germany Email: vogelc@ipfdd.de Received November 29, 2011; revised December 26, 2011; accepted January 12, 2012 ABSTRACT Catalytic amounts of cesium carbonate are sufficient to initiate the “silyl method”-type step-growth polymerization of phenylene-bis-TMS-ethers and -thioethers with activated aryl fluoride monomers, and can thus be used instead of ce- sium fluoride or potassium carbonate. Cesium fluoride is very hygroscopic and potassium carbonate is generally used in equimolar amounts. The efficiency of catalytic amounts of cesium carbonate is demonstrated by the synthesis of poly(phenylene ether ether ketone) and poly(phenylene sulfide sulfone) examples. Keywords: Cesium Carbonate; Polycondensation; Step-Growth Polymerization 1. Introduction The step-growth polymerization reaction of bis-trime- thylsilyloxy- or bis-trimethylsilylthio-phenylenes 1 with activated aryl fluorides 2, the so-called “silyl method”, has found wide application in the synthesis of poly- phenylene ether (resp. sulfide) ketones and sulfones (see Scheme 1) [1-13]. It involves nucleophilic aromatic sub- stitution reactions on activated aryl halides e.g. 4,4’-di- fluorobenzophenone or 4,4’-difluorodiphenyl sulfone 2. The reaction in solution, e.g. in N-methylpyrrolidin-2- one (NMP) as solvent, is usually carried out in the tem- perature range of 130?C - 200?C [1-9]. Simple heating of a bisphenol bis-trimethylsilyl ether with an activated aryl halide does not result in polycondensation reactions [6]. The step-growth polymerization is usually initiated by adding either equimolar amounts of potassium carbonate -typically