Cyclobutenes containing pendant groups of varying sizes were polymerized via ROMP using Grubbs catalyst 2ndgeneration. The polymerization of these new molecules proceeded with first order kinetics, consistent with a living, well-controlled reaction. The �living� nature of the polymerization was confirmed by chain extension experiments and by the synthesis of diblock copolymers with PDIs below 1.4. This is the first report of the synthesis of diblock copolymers using Grubbs catalysts and cyclobutene monomers. The rate of polymerization depended on the size of the pendant groups in the cyclobutene rings and it decreased as the pendant group size increased. Diblock copolymers of the new cyclobutene monomers and norbornene analogs were prepared with low PDIs. The synthetic methods in this report will allow access to new complex polymeric architectures with a higher density of pendant groups than those possible when using norbornene and cyclooctene derivatives as the starting materials.

Block copolymer synthesis of triazole-bearing cyclobutenes by ring opening methathesis polymerization

248th National Meeting (2014)

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