Multicyclic polyethers with pendant keto groups by polycondensation of silylated 1,1,1‐tris(4‐hydroxyphenyl)ethane

1,1,1‐Tris(4‐trimethylsiloxyphenyl)ethane, (silylated THPE), was polycondensed with 2,4‐difluoroacetophenone and 2,4‐difluorobenzophenone. All polycondensations were performed in N‐methylpyrrolidone with K₂CO₃ as promotor. The feed ratio THPE/difluoroaromat was varied from 1.0:1.3 to 1.0:1.5. Instead of hyperbranched polymers or gels, soluble multicyclic oligo‐ and polyethers were identified as main reaction products by MALDI‐TOF mass spectrometry in all experiments. At feed ratios around 1.0:1.5 multicycles free of functional group were the main products. However, when isomeric a₂‐monomers such as 2,6‐difluoroacetophenone, 2,6‐difluorobenzophenone (or 2,6‐difluorodiphenylsulfone) were used, gelation occurred at feed ratios as low as 1.0:1.1. An explanation of the different cyclization tendencies on the basis of different conformations is discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6233–6246, 2005