Abstract
The mechanism of the polymerization of sulfur-containing aldehydes initiated by AlEt3 or AlEt3—alcohol catalyst systems has been studied. The equimolar reaction of AlEt3 with the aldehyde under polymerization conditions formed Et2AlOR. The polymerization using the monoalkoxides, which were prepared from AlEt3 and the alcohols obtained with the reduction of monomer, was essentially identical with those using AlEt3 itself as initiator at −78°C. In the polymerizations at higher temperatures, −25—−35°C, a linear oligomer was produced together with a dimeric ester and the polymer. From IR, NMR, and, tracer analyses it was found that the oligomers have ester and alkoxy end groups. In the polymerization by AlEt3—t-butyl alcohol(C-14 labeled *ButOH) systems, a radioactive polymer was obtained. These observations can be interpreted in terms of a coordinated anionic mechanism. The possibility of an alternative mechanism, a cationic one, has been examined.
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Yamamoto, N., Yamashita, I. Polymerization of Sulfur-Containing Aldehydes. IV. Mechanism of Polymerization with Organoaluminum. Polym J 7, 50–61 (1975). https://doi.org/10.1295/polymj.7.50
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DOI: https://doi.org/10.1295/polymj.7.50