Macromonomer synthesis. New functionalization methods

Abstract

So far, the syntheses of macromonomers by end‐capping of “living” anionic polymers with unsaturated electrophiles, were not always quantitative. Now, we found that macromonomers with unsaturated end groups can be smoothly prepared with quantitative yields from ω‐hydroxy‐poly(ethyleneoxide)s (PEO) applying methods of peptide synthesis. The intermediate PEO with carboxylic, p ‐toluenesulfonate or chlorocarbonyl end groups were prepared with quantitative yields. They were transformed into the 4‐vinylphenyl substituted PEO macromonomers by reaction with 2‐(4‐vinylphenyl)ethanol or 4‐vinyl‐aniline, in quantitative yields, in the presence of dicyclohexylcarbodiimide and 1‐hydroxybenzotriazole or triethylamine, respectively. PEO with methacryloyl end groups were prepared from ω‐hydroxy‐PEO and 2‐isocyanato ethyl methacrylate. The resulting macromonomers were characterized by determination of the double bond content and by 1 H NMR spectroscopy.