Relative Rates for Plasma Homo- and Copolymerizations of Olefins in a Homologous Series of Fluorinated Ethylenes

The relative rates of plasma (co)polymerizations of ethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene and tetrafluoroethylene (VF(sub x); x = 0-4, respectively) were determined in an rf, capacitively coupled, tubular reactor with external electrodes using identical plasma parameters. The averages of deposition rates obtained by both microgravimetry and ellipsometry were plotted versus the F/C ratios of the monomers or monomer blends. The deposition rates for VF(sub x)(x = 1-3) and 20 monomer blends were all located above a straight line joining the rates for VF(sub 0) and VF(sub 4), following a concave-downward plot of deposition rate versus F/C ratio similar to that reported previously for VF(sub 0)/VF(sub 4) blends. The deposition rates for VF(sub m)/VF(sub n) blends (m = 3 or 4; n = 0-2) were all greater than expected for non-interacting monomers; those for VF(sub 0)/VF(sub 2) and VF(sub 1)/VF(sub 2) blends were all lower than expected; while those for VF(sub 0)/VF(sub 1) and VF(sub 3)/VF(sub 4) blends fen on a straightline plot versus F/C ratio, indicative of apparent non-interaction between monomers. The mechanisms for plasma (co)polymerizations of VF(sub x) monomers responsible for the wide range of relative deposition rates remain to be elucidated.