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SynopsisA number of poly(viny1 alkyl ethers) and poly(viny1 alkyl sulfides) of reasonably high molecular weight were prepared. Glass transformation temperatures T, of the various polymers were measured dilatometrically. In general, the T , value decreased with increasing length of the n-alkyl group. Data relating T , values of poly(viny1 n-alkyl ethers) with length of n-alkyl group were treated in terms of free volume concepts of the liquid state. Branching on the alkyl group of the polymer increased the T , value. Poly(viny1 n-alkyl sulfides) had T , values about 35°C. higher than their oxygen analogs. A comparison of poly(viny1 n-alkyl ethers) and polymers of normal a-olefins showed that the ether group and methylene group in side chains were equivalent in influencing the glass transformation temperatures. From a comparison of poly( vinyl n-alkyl ethers) and poly(n-alkyl methacrylates) it is concluded that the nature of the backbone is important in determining the ease with which side chain crystallization takes place.

Natural rubber-sulfur-diphenylguanidine vulcanizates were allowed to react with triphenylphosphine under nitrogen to convert polysulfidic crosslinks principally to di- and monosulfidic crosslinks and to assess the effect of this change in the chemical nature of the crosslinks on tensile strength, flex life, and oxygen absorption characteristics. The vulcanizates were analyzed for organically combined sulfur and polysulfidic sulfur. Data obtained by this approach were treated statistically and showed that polysulfidic crosslinks are not essential for attaining high tensile strength or superior flex life. In another approach, polysulfidic crosslinks were introduced into dicumyl peroxide-cured vulcanizates containing carbon-carbon crosslinks to yield two-stage vulcanizates. Data for these vulcanizates fitted the curve of tensile strength as a function of 300% modulus for the precursor samples. It was further shown that the reduced failure envelope for natural rubber gum vulcanizates is independent of the type and relative concentration of chemical crosslinks. An interesting observation was made that the tensile strengths of dicumyl peroxide-cured samples were enhanced on extraction with acetone. Vulcanizates which had lost 95–99 per cent of their polysulfidic sulfur due to reaction with triphenylphosphine exhibited significantly lower rates of oxygen absorption at 100° C as compared to the untreated vulcanizates. This suggests that polysulfidic structures in the original vulcanizates act as oxidation initiators.

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