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Published June 10, 2020 | Supplemental Material
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Ru-Catalyzed, cis-Selective Living Ring-Opening Metathesis Polymerization of Various Monomers, Including a Dendronized Macromonomer, and Implications to Enhanced Shear Stability


An unsaturated polymer's cis/trans-olefin content has a significant influence on its properties. For polymers obtained by ring-opening metathesis polymerization (ROMP), the cis/trans-olefin content can be tuned by using specific catalysts. However, cis-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 cis-selective controlled living ROMP of various endo-tricyclo[^(2,5)]deca-3,9-diene and various norbornene derivatives using a fast-initiating dithiolate-chelated Ru catalyst. Polymers with cis-olefin content as high as 99% could be obtained with high molecular weight (up to M_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 cis-olefin content for the first time. Furthermore, owing to the successful control over the stereochemistry and narrow dispersity, we could compare cis- and trans-rich polynorbornene and found the former to have enhanced resistance to shear degradation.

Additional Information

© 2020 American Chemical Society. Received: March 11, 2020; Published: May 11, 2020. This paper is dedicated to Professor Heon Kang at SNU on his 65th birthday and his life-long achievement in research and education. We thank the Creative Research Initiative Grant and Nano-Material Technology Program through NRF, Korea, for financial support. G.I.P. is grateful for the financial support from the NRF of Korea, Young Investigator Grant (Grant 2018R1C1B6003054). R.H.G. acknowledges funding form the Office of Naval Research (N00014-14-10650), NIH (GM031332), and NSF (CHE-1502616). T.S.A. recognizes NSF for support through a Graduate Research Fellowship. Materia, Inc. is thanked for their generous donation of Ru catalyst precursors. The authors declare no competing financial interest.

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