Click chemistry has been used to prepare a range of novel polymers with pendant carboxylic acid side groups. Four azido carboxylic acids, either mono- or difunctional and aliphatic or aromatic, have been prepared and thoroughly characterized. Extensive model reactions with 1-ethyl-4-hydroxybenzene, the simplest model for poly(4-hydroxystyrene), and the four azido carboxylic acids have been conducted to establish the proper reaction conditions and provide an analytical frame for the corresponding polymers. Poly(4-hydroxystyrene) moieties in three different polymers-poly (4-hydroxystyrene), poly(4-hydroxystyrene-co-methyl methacrylate), and poly(4-hydroxystyrene-b-styrene) - have been quantitatively transformed into oxypropynes by the use of either Williamson or Mitsunobu strategies and subsequently reacted with the azido carboxylic acids. Detailed differential scanning calorimetry investigations of all the polymers in general exhibit [when poly(4-hydroxystyrene) is a substantial part] significant changes in the glass-transition temperature from the polar poly(4-hydroxystyrene) (120-130 degrees C) to the much less polar alkyne polymers (46-60 degrees C). A direct correlation between the nature of the pendant groups in the derivatized polymers and the glass-transition temperature has emerged: the aromatic carboxylic acids give high glass-transition temperatures (90-120 degrees C), and the aliphatic carboxylic acids give lower glass-transition temperatures (50-65 degrees C). (c) 2006 Wiley Periodicals, Inc.