Control of Diffusion and Conformation Behavior of Methyl Methacrylate Monomer by Phenylene Fin in Porous Coordination Polymers

Abstract

Radical polymerization in nanoscale channels of porous coordination polymers has been explored as a promising technique to control the properties of product polymers. In particular, tacticity of poly(methyl methacrylate) was successfully controlled by utilizing one-dimensional channels of [M2(L)2TED]n type of porous coordination polymers by changing the dicarboxylate ligand L. Toward understanding the atomistic mechanism of this tacticity control, we computationally studied the behavior of methyl methacrylate monomers in the one-dimensional channels by molecular dynamics simulations. Smooth monomer diffusion in the direction along the channel was shown as expected from the channel shape. In addition, we confirmed that the monomers can pass through the narrow apertures between the channels and can diffuse slowly in the direction perpendicular to the channel. In the channels, the ratio of the s-trans and s-cis conformations of the monomers is different from that in monomer liquid. We found two factors affec...