Date of Award


Document Type


Degree Name

Doctor of Philosophy (PhD)



Committee Member

Dr. Joseph S. Thrasher, Committee Chair

Committee Member

Dr. Darryl D. DesMarteau

Committee Member

Dr. Stephen E. Creager

Committee Member

Dr. William T. Pennington


The addition of a pilot-scale tetrafluoroethylene (TFE) polymerization facility at Clemson University has enabled this academic institution to not only prepare TFE in kilogram quantities but also to store it and copolymerize it in safe conditions. The facility is used to prepare equimolar mixtures of TFE/CO2 from the pyrolysis of potassium perfluoropropionate in approximately quantitative yields. The TFE is separated from the mixture and stabilized by D-limonene by scrubbing CO2 from the aforementioned mixture. With the development of high technology software and hardware, the facility has been used to study the relative reactivity ratios of various polymerizations systems like the copolymerization of TFE with sulfonyl fluoride-substituted vinyl ethers [(perfluoro-3-oxa-4-pentene sulfonyl fluoride [DOW monomer] and perfluoro-2-(2-fluorosulfonylethoxy) propyl vinyl ether [PSEPVE]), methyl perfluoro(4-oxa-5-hexanoate) (DEVE), and perfluoro 8-cyano-5-methyl-3,6-dioxa-1-octene (8CNVE)], and vinylidene difluoride (VDF), in the presence and absence of CO2. Some results from these studies as well as further details on the facility will be presented.

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