Abstract: | Stereospecific polymerization of acetaldehyde was examined by using four possible purified diethylaluminum butoxides, (Et2AlOBu)2 Bu = n-, i-, sec-, or tert-Bu], as catalyst. These catalysts gave isotactic polyacetaldehyde quantitatively irrespective of the degree of branching of the butyl group, only when an optimum amount of water (about 0.03 mole/mole of catalyst) was added to the purified acetaldehyde monomer. Quite similar results were obtained for organozinc catalysts. These results indicate that water is an indispensable cocatalyst in the polymerization reaction with organoaluminum and zinc catalysts. An novel coordinate cationic mechanism was proposed for the stereospecific polymerization of acetaldehyde with organoaluminums, based on the above phenomena and on the inactivation of the catalyst by forming a complex with a strong Lewis base. |