Résumé
The controlled radical polymerization of butadiene initiated with 2,2′‐azoisobutyronitrile (AIBN) and in the presence of 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) is presented. The produced oligomers which have number average degrees of polymerization ranging between 3 and 12 were characterized by NMR. This led to the determination of both the end‐groups and the functionality. The hydrolysis of these oligomers yields α‐hydroxy‐ω‐cyano‐polybutadiene. 13C and 1H NMR spectra of these products exhibit two characteristic signals of hydroxymethyl groups. The mechanism of the polymerization allows the assignments to cis‐ and trans‐CH2CH=CH—CH2OH groups. In fact, this method also shows that geraniol end‐groups are negligible in commercially available products obtained by the polymerization initiated with hydrogen peroxide.