5,5',6,6'-Tetrahydroxy-3,3,3',3-tetramethyl spirobisindane (TTSBI) was polycondensed with 4,4'-dichlorodiphenyl sulfone (DCDPS) or with 4,4'-bis(4-chlorophenyl sulfonyl) biphenyl (BCSBP) in DMSO. Concentration and feed ratio were optimized to avoid gelation and to obtain a maximum yield of multicyclic polyethers free of functional groups. Regardless of these reaction conditions, only low fractions of perfect multicycles were obtained from DCDPS apparently due to steric hindrance of ring closure. Under the same conditions high fractions of perfect multicycles were achieved with the longer and more flexible DCSBR The reaction products were characterized by MALDI-TOF mass spectrometry, H-1-NMR spectroscopy viscosity, and DSC measurements. Relatively low glass transition temperatures (T(g)s approximate to 160-175 degrees C) were found. (C) 2008 Wiley Periodicals, Inc.