Influence of monomer structure and catalyst concentration on topological transition and dynamic properties of dicarboxylic acid‐epoxy vitrimers

This study delineates the dependence of thermophysical behavior of acid‐epoxy vitrimers on their formulation. The stress relaxation due to the bond exchange reaction and the glass transition temperature of acid epoxy vitrimers are investigated, with respect to the influence of catalyst content and acid chain length. This is carried out for a range of dicarboxylic acids and catalyst concentrations formulated and characterized using calorimetry and dynamic mechanical analysis. The influence of acid chain length on the bond exchange rate, topological transition, and glass transition temperatures of the vitrimers is found to be significant. The activation energy of the exchange reaction varies over a wide range from 73 to 104 kJ/mol and the topology freezing temperature from 66 to 136°C with the behavior governed by the interplay between crosslinking density, network flexibility and density and distance of functional groups, with an increase of catalyst concentration leading to lower topological transition temperature and the dependence on chain length showing non‐monotonic behavior. The glass transition decreases by about 30°C as the carbon chain length increases from 6 to 14 carbons due to enhanced monomer flexibility and is not affected by the concentration of catalyst.