Abstract Ehylene can be polymerized at low pressures in a radio-frequency glow discharge. The form of the resulting polymer may be a powder at low pressure (1 to 2 Torr) and low monomer feed rate (10 to 40 cc/min), a colorless film at low pressure and high feed rate (70 to 90 cc/min), or an oil at high pressure (4 to 5 Torr) and high feed rate. The powder and film forms of plasma-polymerized ethylene are insoluble in common organic solvents, indicating a highly cross-linked structure. The oily products, however, are soluble in acetone and xylene. Chemical evidence indicates that the oil is most likely composed of highly branched oligomers of ethylene. Mass spectrometric analysis of the gaseous effluents show that under film-forming conditions the only hydrocarbon species observable are those derived from ethylene. The powder- and oil-forming conditions, on the other hand, yielded oligomeric species. On the basis of this evidence, a mechanism for the plasma-polymerization of ethylene is proposed.
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