Modification of Poly(maleic anhydride)-Based Polymers with H2N-R Nucleophiles: Addition or Substitution Reaction?

Reacting poly(maleic anhydride)-based polymers with H2N-R nucleophiles is a flexible and highly effective approach for preparing a variety of multifunctional, multicoordinating, and multireactive polymers. The exact transformation of the anhydride ring during this addition reaction is still an open question. In this report, we characterize the transformation of a representative block copolymer, poly(isobutylene-alt-maleic anhydride), with a few H2N-R nucleophiles. In particular, we test the effects of varying a few reaction parameters/conditions (e.g., temperature, solvent, reaction time, and addition of thionyl chloride) on the nature of the anhydride transformation and bond formed between the polymer and the lateral R groups. The resulting polymers are characterized using a combination of analytical techniques including FT-IR, one- and two-dimensional NMR, and gel electrophoresis. We find that the ring opening transformation occurs under mild conditions. Conversely, cyclic imide transformation can take place for reactions carried out at high temperature (e.g., in DMF under refluxing conditions). We also find that use of a protic solvent, such as methanol, or addition of thionyl chloride (SOCl2) to the reaction mixture under refluxing conditions can promote cyclic imide transformation. The cyclic imide transformation is nonetheless partial, as carboxyl groups could still be accounted for in the resulting compounds. Depending on the type of transformation, the resulting polymer can exhibit a few distinct properties, such as net charge buildup along the chain, or the appearance of weak UV-vis absorption and fluorescence properties. These findings are useful for understanding the properties exhibited by polymer materials prepared via this flexible and highly effective route using anhydride containing polymers and oligomers.