Macromolecules, Vol.36, No.15, 5551-5558, 2003
Cyclic hyperbranched poly(ether ketone)s derived from 3,5-bis(4-fluorobenzoyl)phenol
3,5-Bis(4-fluorobenzoyl)phenol was polycondensed under various reaction conditions. Low molecular weights were obtained (M-n < 8000 Da), and MALDI-TOF mass spectrometry indicated that the chain growth was limited by cyclization. In the best mass spectra the cyclic, hyperbranched poly(ether ketone)s were detectable up to masses around 14 000 Da. When 4,4'-difluordiphenyl sulfone was added, star-shaped polymers having a diphenyl sulfone star center were formed, but cyclization was not completely suppressed. The results were compared to those obtained from "linear polycondensations" based on 4,4'-difluorobenzophenone (DFBP) and 4-tert-butyleatechol or bisphenol A. The poly(ether ketone)s of DFBP had also low molecular weights and contained high fractions of cycles. It is concluded that also in the case of hyperbranched polymers cyclization competes with propagation at any stage of the polycondensation at any concentration. Therefore, the fundamental trend of any "ab(n)" polycondensation is the formation of star-shaped polymers having a cyclic core and hyperbranched star arms.