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Tiglic acid esters are naturally derived olefins of pleasant odor but incapable of undergoing free-radical polymerization due to the steric hindrances conferred by the β-methyl group. In an effort to incorporate these green olefins in well-defined (co)polymers, we first established that methyl tiglate, the simplest tiglic acid ester, could not be polymerized using controlled polymerization techniques either, and we then introduced it in a methacrylate monomer, 2-(methacryloyloxy)ethyl tiglate (MAET), which could smoothly undergo group transfer polymerization (GTP) to yield linear polymers of narrow molecular weight distributions. Subsequently, amphiphilic and double-hydrophobic block copolymers, as well as a star polymer of MAET were obtained by its sequential GTP with 2-(dimethylamino)ethyl methacrylate, methyl methacrylate, and ethylene glycol dimethacrylate, respectively. Finally, polyMAET was selectively oxidized.

Seven cyclolinear polymers bearing the tertiary‐butyl α‐(hydroxymethyl)acrylate (TBHMA) ether dimer were prepared using reversible addition–fragmentation chain transfer (RAFT) polymerization. Of the seven polymers, five were cyclolinear homopolymers of the TBHMA ether dimer with different degrees of polymerization, one was an “arm‐first” star homopolymer, and the other was an amphiphilic linear copolymer based on the positively ionizable hydrophilic 2‐(dimethylamino)ethyl methacrylate (DMAEMA) and the TBHMA ether dimer. For comparison, two more polymers were prepared using RAFT polymerization where the TBHMA ether dimer was replaced by tertiary‐butyl methacrylate (tBuMA). In particular, an amphiphilic linear DMAEMA–tBuMA diblock copolymer and a tBuMA arm‐first star homopolymer were also synthesized. All polymers were characterized in terms of their molecular weights and composition using gel permeation chromatography and 1H NMR spectroscopy, respectively. Subsequently, the tertiary‐butyl groups of the TBHMA ether dimer units and those of the tBuMA units were cleaved by hydrolysis to yield carboxylic acid groups. The successful removal of the tertiary‐butyl groups was confirmed using 1H and 13C NMR and attenuated total reflectance‐Fourier transform infrared spectroscopies. The hydrolyzed (co)polymers exhibited pK values of the carboxylic acid groups of around 4.5, and glass transition temperatures, Tg, of around 200 °C, which were 50 °C higher than those of their nonhydrolyzed precursors. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012