TY - JOUR
T1 - The mechanism of Zinc(II)-Mediated Vulcanization Uncovered; Theoretical and Experimental Evidence.
AU - Nieuwenhuizen, P.J.
AU - Ehlers, A.W.
AU - Haasnoot, J.G.
AU - Janse, S.R.
AU - Reedijk, J.
AU - Baerends, E.J.
PY - 1999
Y1 - 1999
N2 - The mechanism of cross-link formation in sulfur vulcanization mediated by bis(dimethyldithiocarbamato)zinc(II), ZDMC, has been uncovered, utilizing a combination of Density-Functional calculations and model experiments. These studies have revealed that, in a three-stage process, ZDMC exhibits a unique combination of catalytic activity: (1) It mediates the reaction between sulfur and rubber. This is achieved by incorporating sulfur atoms in the zinc-dithiocarbamate ring and inducing their insertion into an allylic C-H bond via an ene-like reaction. This ene reaction yields a rubber-bound polythiothiol and is only slightly endothermic, even though an activation energy of ~90 kJ mol
AB - The mechanism of cross-link formation in sulfur vulcanization mediated by bis(dimethyldithiocarbamato)zinc(II), ZDMC, has been uncovered, utilizing a combination of Density-Functional calculations and model experiments. These studies have revealed that, in a three-stage process, ZDMC exhibits a unique combination of catalytic activity: (1) It mediates the reaction between sulfur and rubber. This is achieved by incorporating sulfur atoms in the zinc-dithiocarbamate ring and inducing their insertion into an allylic C-H bond via an ene-like reaction. This ene reaction yields a rubber-bound polythiothiol and is only slightly endothermic, even though an activation energy of ~90 kJ mol
UR - https://www.scopus.com/pages/publications/0033550527
UR - https://www.scopus.com/inward/citedby.url?scp=0033550527&partnerID=8YFLogxK
U2 - 10.1021/ja982217n
DO - 10.1021/ja982217n
M3 - Article
SN - 0002-7863
VL - 121
SP - 163
EP - 168
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -
