Step-growth polymerization of perfluoro-vinyl ether, -cycloalkenes, and -acyclic alkenes with bisphenols containing variable polycyclic aromatic cores

This dissertation reports the synthesis and characterization of semi-fluorinated polymers derived from the polymerization of bisphenols with fluoroalkenes. A series of diverse bisphenols were chosen from popular commercial bisphenols and new polycyclic aromatic hydrocarbon (PAH) derived bisphenols requiring synthesis. Step-growth condensation polymerization of bisphenols with three different fluoroalkene types was performed while probing polymerization conditions and the structure/properties relationship of the resulting fluoropolymers. The fluoroalkene monomers were chosen from bis(trifluorovinyloxy)biphenyl (TFVE), perfluorocyclohexene (PFCH), and perfluoro acyclic monomers, namely, perfluoro(4-methyl-2-pentene) and 1-perfluoroheptene to undergo this chemistry. This work is divided into four parts based on the polymerization methodology. The first section focuses on the development of a new class of fluorinated arylene vinylene ether (FAVE) and their chain extended polymers prepared via base-catalyzed step-growth polymerization of PAH bisphenols with the TFVE monomer. These reactions afforded polymers containing controlled terminal and enchained fluoroalkenylenes for latent reactivity such as post polymerization functionalization, chain extension, and/or crosslinking. In general, these PAH cores resulted in polymers with improved thermal properties The second portion describes the investigation of step-growth addition/elimination polymerizations of PAH bisphenols and PFCH to prepare a new class of fluoropolymers containing alternating rigid PAH linkages and enchained PFCH vinylene ether moieties in the backbone. The third section covers the preparation and characterization of semi-fluorinated poly(aryl ether sulfone)s by nucleophilic addition/elimination reactions of PFCH with sulfone bisphenols. From commercially bisphenols combined with PAH bisphenols, we introduced the industrially valuable and property enhancing diaryl sulfone unit in a series of semi-fluorinated copolymers. This modular approach greatly expands access to partially fluorinated aryl ether sulfone polymers intended for high performance applications in optoelectronics, separation/purification membranes, and composites. Finally, in the fourth section, a new class of semifluorinated polymers was synthesized via nucleophilic addition/elimination reactions of acyclic perfluoroalkenes with bisphenols. In particular, environmental concerns for biopersistent and highly regulated perfluorooctanoic acid (PFOA) is the driver for using perfluoroheptene, which is derived cleanly by the decarboxylation of these pollutants in one step. This provided a new class of semi-fluorinated materials with promising properties including thermal stable, processability, and transparent film formation