Polyoctenylenes and polydodecenylenes prepared by the methathesis reaction exhibit a bimodal molecular weight distribution. The low molecular weight fraction consists of cyclic oligomers, the high molecular weight fraction is assumed to contain linear polymers. The distribution of cyclic oligomers together with the polymer material indicates a ring-chain equilibrium. The slope of the plot log Kx (molar cyclization equilibrium constant) vs. log x (degree of polymerization) is close to −2,5 as predicted by the Jacobson and Stockmayer theory for unstrained macrocycles. Polyoctenylene und Polydodecenylene, dargestellt mit Hilfe der Metathese-Reaktion, weisen eine bimodale Molekulargewichtsverte…

The thermal behavior of cycloalkanes (CH2)n with 12 ≤ n ≤ 84 prepared by metathesis reaction of cyclododecene, GPC separation of the oligomers, and hydrogenation has been investigated. The molar enthalpies of fusion being lower by a certain amount than those of the corresponding n-alkanes are a linear function of the chain length n. The entropy of fusion per CH2 increases with chain length in a not-linear mode (when plotted vs. 1/n). The melting points of the cycloalkanes are lower than those of the corresponding n-alkanes, the difference becoming smaller with increasing chain length.

The mass spectra of cycloolefins (C12xH22x), cycloalkanes (C12xH24x), and unbranched alkanes are compared. The most prominent fragmentation series are CnH2(n–p)−1⊕, CnH2n − 1⊕, and CnH2n+1⊕, respectively. The intensity of the molecular ion peak decreases in the order given.