Summary: Anionic polymerizations of hydroxyl-protected α-(hydroxymethyl) acrylates were investigated. The methyl ester with methoxymethyl (1-MOM) and allyl (1-allyl) protecting groups were polymerized by isopropyl α-lithioisobutyrate (Li-iPrIB) in toluene at 78 °C, affording highly isotactic polymers. Similarly, the polymerization of ethyl ester (2-MOM) gave an isotactic polymer, while those of t-butyl (3-MOM) and isobutyl (4-MOM) ester did not form any polymeric products. The hydrolysis of poly(2-MOM) in acidic conditions resulted in the deprotection of MOM group, although the acid also catalyzed the ester exchange between the neighboring units to form lactone units, as observed by 1 H NMR analysis, IR spectroscopy and thermogravimetric analysis. A film of poly(2-MOM) exposed to HCl vapor for 2 h became insoluble in any organic solvents due to the lactonization in solid state.

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