Abstract
An essential structure of the intermediate generated from zinc oxide and stearic acid during sulfur cross-linking reaction of isoprene rubber is proposed using time-resolved zinc K-edge X-ray absorption fine structure and infrared spectroscopies in situ. The structure is dominantly a bridging bidentate zinc/stearate complex, the molar ratio of the zinc ion to stearate and the coordination number of which are unexpectedly 1:1 and 4, respectively. Combination with a density functional calculation for identifying the intermediate predominantly suggests that its most possible structure is (Zn2(μ-O2CC17H35)2)2+(OH–)2·XY, where X and Y are water and/or a rubber segment. This intermediate has been unknown despite the long history of rubber science and technology. The newly observed zinc/stearate complex may play a role to accelerate the sulfur cross-linking reaction of rubber like an enzyme because of the high Lewis activity of the zinc ion.
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