Ru-Catalyzed, <i>cis</i>-Selective Living Ring-Opening Metathesis Polymerization of Various Monomers, Including a Dendronized Macromonomer, and Implications to Enhanced Shear Stability

Abstract

An unsaturated polymer's <i>cis</i>/<i>trans</i>-olefin content has a significant influence on its properties. For polymers obtained by ring-opening metathesis polymerization (ROMP), the <i>cis</i>/<i>trans</i>-olefin content can be tuned by using specific catalysts. However, <i>cis</i>-selective ROMP has suffered from narrow monomer scope and lack of control over the polymerization (giving polymers with broad molecular weight distributions and prohibiting the synthesis of block copolymers). Herein, we report the versatile <i>cis</i>-selective controlled living ROMP of various <i>endo</i>-tricyclo[4.2.2.0^2,5]deca-3,9-diene and various norbornene derivatives using a fast-initiating dithiolate-chelated Ru catalyst. Polymers with <i>cis</i>-olefin content as high as 99% could be obtained with high molecular weight (up to <i>M</i>_n of 105.1 kDa) and narrow dispersity (<1.4). The living nature of the polymerization was also exploited to prepare block copolymers with high <i>cis</i>-olefin content for the first time. Furthermore, owing to the successful control over the stereochemistry and narrow dispersity, we could compare <i>cis</i>- and <i>trans</i>-rich polynorbornene and found the former to have enhanced resistance to shear degradation.