Advancing from unimechanism polymerization to multimechanism polymerization: binary polymerization

Polymerizations with multiple mechanisms performed simultaneously are promising but very challenging. As the key limitation, the complicated mutual influence between different mechanisms can be hardly defined and measured. Herein we establish a universal framework for the assessment of mutual influence between different mechanisms using binary polymerization for demonstration. The kinetics and thermodynamics of polymerization with two mechanisms are compared with the corresponding homopolymerization and the difference is expressed by a hybrid function. The hybrid function is composed of a hybrid parameter that describes the extent of mutual influence and a function that describes necessary conditions for mutual influence to occur. The extent of mutual influence can be calculated using kinetic and thermodynamic data without details of reaction mechanisms, for the first time providing a straightforward method to assess the mutual influence between different polymerization mechanisms. We envision that the method has potential in more complex systems with multiple mechanisms/monomers with mutual influence.