Polymerization in an electrodeless glow discharge. III. Organic compounds without olefinic doublebond

The rates of polymer deposition from various organic compounds which do not contain an olefinic doublebond in an electrodeless glow discharge were studied. The polymerization rates of these unconventional monomers are by and large similar to those of olefinic monomers reported in the previous study (part II). The rate of polymer deposition R0 from pure monomer flow can be characterized, according to the analysis used in part II, by Ro = apM2 and R0 = kFw, where pM is the vapor pressure of the monomer, Fw is the weight basis flow rate of the monomer. Type A monomers which predominantly polymerize and type B monomers which decompose in a glow discharge were also found with these unconventional monomers. The effects of structural factors on the values of a amd k and on the classification of types A and B were examined. These structures and groups—aromatic, heteroaromatic, nitrogen‐containing (e.g., >NH,NH2,CN), Si‐containing, and olefinic doublebond—favor the polymerization. These structures and groups—oxygen‐containing chlorine, aliphatic hydrocarbon chains, and cyclic hydrocarbon chains—favor the decomposition of the monomer in a glow discharge. It is postulated that the polymerization of organic compounds proceed by the recombination of excited species (probably free radicals) created by glow discharge and reexcitation followed by further recombinations in the vapor phase and at the interface.