Linear Cyclobutane-Containing Polymer Synthesis via [2 + 2] Photopolymerization in an Unconfined Environment under Visible Light.

The [2 + 2] photopolymerization of diolefinic monomers is an appealing approach for the construction of polymeric materials. Herein, we demonstrate that the establishment of an effective donor-acceptor conjugation by introducing electron-donating alkoxy groups at appropriate positions of the benzene ring could activate p-phenylenediacrylate (PDA), thus enabling the development of the first solution [2 + 2] photopolymerization of such monomers under the irradiation of visible light. Variation on the alkoxy groups and the ester parts could allow access to a series of linear cyclobutane-containing polymer products with high molecular weight (up to 140 kDa) and good solubility in common solvents. Further, temporal control and postpolymerization modification with preinstalled pendant C═C bonds via thiol-ene click reaction are also demonstrated with this [2 + 2] photopolymerization system.