Ethylene‐co‐vinyl acetate copolymer crosslinking through ester–alkoxysilane exchange reaction catalyzed by dibutyltin oxide: mechanistic aspects investigated through model compounds by multinuclear NMR spectroscopy

It was shown that the crosslinking of ethylene‐co‐vinyl acetate (EVA) copolymer by a tetraalkoxysilane in molten state, in the temperature range 100–250 °C, was obtained only in the presence of dibutyltin oxide. At this temperature EVA pendant ester groups readily react with dibutyltin oxide to give a dimeric 1‐alkoxy‐3‐acetoxytetrabutyldistannoxane distributed along the polymer chains. The exact role of this tin compound in the ester–alkoxysilane reaction was elucidated through reactions of the tetraalkoxysilane with parent tin compounds: tributylethoxytin, dimeric diacyloxydistannoxane and finally a dimeric 1‐alkoxy‐3‐acyloxydistannoxane, obtained by reaction of the dibutyltin oxide with a model ester instead of the EVA‐ester pendant group. Ligand exchanges on tin atoms characterized by multinuclear NMR spectroscopy (¹H, ¹³C and ¹¹⁹Sn) showed that substitutions were selective and concern only the exo‐cyclic tin ligand (OR or OCOR′) without alteration of the dimeric distannoxane structure. Furthermore, these ligand exchanges occurred at room temperature. This approach with model compounds gave evidence that the crosslinking occurred via an alkoxy‐Sn/alkoxy‐Si exchange on the exo‐cyclic sites of the distannoxane structure formed in situ. This distannoxane was shown to be an efficient catalyst of this transesterification. The temperature of formation of this catalytic species governed the temperature of the beginning of the crosslinking reaction. Copyright © 2004 Society of Chemical Industry