Crosslinking of polymer networks and their attachment to surfaces is a powerful tool to modify the interaction between a material and the environment. Many methods to achieve polymer networks include crosslinking during polymerization or the use of external reagents. Some disadvantages, however, are that such materials cannot be processed and that reagents may remain in the network, which can diffuse into the environment. A versatile way to overcome these challenges is the C,H insertion based crosslinking (CHic) reaction. A few dormant crosslinker molecules are integrated in a polymer which form reactive groups. Through UV or thermal activation these groups react with any C,H group in direct vicinity to form a network. Simultaneously surface attachment occurs when the surface has C,H bonds. Reactive intermediates, which undergo this type of reaction, are ketyl biradicals, nitrenes or carbenes. One way to generate carbene intermediates is upon thermal or photochemical activation of diazo-groups. This activation is controllable to a certain extend through the chemical environment of the diazo group. With the use of acceptor or donor groups, it is possible to tune the thermal activation parameter through stabilization or destabilization of the diazo group. The photochemical behaviour is also controllable using the [endif]--&gt; electron system to go from UV-activation to activation through visible light. Through the control of diazo decomposition, it is possible to tune the crosslinker to the desired activation for the network formation.

Tunable thermal and photochemical crosslinking of CHic-able diazo-groups containing polymers

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.