Abstract

The viscoelastic properties of various crosslinked natural rubbers, NR, were investigated by mechanical spectroscopy. The glass transition temperature, Tg, was found to be dependent on both the crosslink density and the crosslink type. Higher values of Tg were obtained for sulfur-crosslinked NR than for peroxide-crosslinked NR at the same crosslink density. The greater influence of the sulfur content on Tg may be attributed to polysulfidic crosslinks and cyclic sulfide structures favored at high sulfur contents. Sulfur-vulcanized NRs with monosulfidic crosslinks, favored at relatively high accelerator/sulfur ratios, have properties more similar to the peroxide-cured NR with simple carbon(SINGLE BOND)carbon crosslinks covalent bonds, resulting in only small shifts in Tg. A qualitative analysis of monosulfidic crosslinks and polysulfidic structures was performed with 13C solid-state NMR spectroscopy. The storage modulus, E′, in the rubbery plateau region increased with increasing crosslink density. However, the crosslink type did not influence the moduli values as much as it influenced the Tg values. Different methods of detecting the crosslink density were also discussed. © 1996 John Wiley & Sons, Inc.

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