The Far Infrared Spectrum of Vulcanized Natural Rubber.

Abstract

Earlier studies of the infrared spectra of natural rubber and some vulcanizates of rubber have been extended into the 650 to 33 cm-1 far infrared region. Some of the absorption bands originating in the crystalline portion of unvulcanized rubber have been studied by using polarized radiation and samples oriented by stretching. Vulcanization of rubber with sulfur alone produces a general weakening of all absorption bands and no new absorptions. Vulcanization with sulfur and an accelerator also results in a reduction in intensity of the rubber absorptions, but is accompanied by the appearance of new bands. When the accelerator is tetramethylthiuram disulfide (TMTD) the new bands are probably indicative of a thiocarbamate structure. When zinc dibutyldithiocarbamate is used as an accelerator a band probably due to zinc sulfide occurs. Vulcanization with TMTD alone produces only slight changes in the far infrared spectrum. However, when TMTD is used in the presence of zinc oxide a reaction occurs in which zinc dimethyldithiocarbamate (ZnDMDC) is formed. After vulcanization for a short period of time strong TMTD bands remain, but after long vulcanization the TMTD bands are replaced by ZnDMDC bands.