Cyclic anhydride ring opening reactions: theory and application

The development of a zero net shrinkage dental restorative material based upon a polymer-bioactive-glass composite requires a second-phase material that expands. This study details the mechanisms of organic cyclic anhydride ring expansion via hydrolysis. Six cyclic anhydrides were used to represent potential side groups, each of which could be an expanding phase or component. Maleic, 4META, tetrahydrophthalic, norbornene, itaconic, and succinic anhydrides were modeled using the Austin method (AM1), a semi-empirical molecular orbital method. The reaction pathways were determined for the anhydride ring opening reaction to form an acid for each case. The activation barriers (Ea) for the ring openings were found from the transition state geometries wherein only one imaginary eigen value in the vibration spectrum existed (a true saddle point). In each case the reaction pathway included the hydrogen bonding of a H2O molecule to the ring, weakening of the C-O bridging bonds of the ring, and, finally, the dissociation of the H2O, forming two carboxyl groups and opening the ring. The activation for the ring openings are +34.3, +36.9, +40.6, +43.1, +45.9, and +47.7 kcal/mol, respectively. The volumetric expansion of the anhydrides was estimated based upon the dilation of C-O-C atomic distances. The dimensional change was found to be 24.0%, 24.0%, 19.1%, 20.3%, 20.8%, and 17.9% for the anhydride rings, respectively. Finally, it was found that a linear correlation exists between the cyclic anhydride C-O asymmetric rocking (as-v) vibration and the activation energy (Ea) for hydrolysis to an acid. This may be used as an experimental indicator of a cyclic anhydride's activity.