Syndiotactic and isotactic poly(tert‐butylethylene oxide)

The rate of polymerization of t‐BuEO by t‐BuOK in DMSO is about one‐tenth that of propylene oxide. The slow rate of propagation was accompanied by considerable chain transfer. In the absence of solvent, the polymer obtained was crystalline, different from the isotactic form and therefore must be syndiotactic. The NMR spectra indicate the isotactic polymer exists in solution preferentially in the skew1 form, while syndiotactic is about 60% skew1, 40% skew2. Amorphous polymer accompanying isotactic exists about 50% in the trans conformer, by NMR data.