Surface-initiated, ring-opening metathesis polymerization: Formation of diblock copolymer brushes and solvent-dependent morphological changes

In this article, we report the formation of diblock copolymer brushes on a gold surface by surface-initiated, ringopening metathesis polymerization (SI-ROMP) with the newly developed ruthenium catalyst [(H₂IMes)(3-Br- py)₂-(Cl)₂Ru=CHPh]. Taking advantage of the highly improved activity of the ruthenium catalyst and the rapid initiation step of ROMP, we successfully formed thin films of well-defined block copolymers with 5-norbornene-2-endo,3-endo-dimethanol and norbornene carboxylic acid methyl esters (44:56 endo/exo). The catalyst was found to be active enough to polymerize endo isomers of norbonene derivatives from the surface as well as to form diblock copolymer brushes. SI-ROMP of diblock copolymers from the surface was confirmed by ellipsometry, infrared spectroscopy, and X-ray photoelectron spectroscopy. After the formation, the polymer-grafted substrates were immersed in various solvents, and the selective swelling characteristics of polymer brushes were investigated by atomic force microscopy.