Poly(cyclosilane) Postpolymerization Hydrosilylation

Coschigano, Marissa G.; Gregory, Sydney L.; Catazaro, Jonathan; Rossini, Aaron J.; Klausen, Rebekka S.

doi:10.1021/acs.macromol.3c02110

Title: Poly(cyclosilane) Postpolymerization Hydrosilylation

Journal Article · 19 April 2024 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.3c02110 · OSTI ID:2338167

Coschigano, Marissa G. ^[1]; Gregory, Sydney L. ^[2]; Catazaro, Jonathan ^[2];

^[3];

^[2]

Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkins University
Johns Hopkins Univ., Baltimore, MD (United States)
Ames Lab., and Iowa State Univ., Ames, IA (United States)

Postpolymerization functionalization is a key strategy in the diversification of polymeric materials for the conferral of tailored properties. Poly(cyclosilane)s are structurally complex polymers with an all-silicon backbone, featuring a periodic array of hydrido (Si–H) side chains that are potentially suitable for postpolymerization functionalization via hydrosilylation. At the same time, classical methods for hydrosilylation employing Pt- or Pd-based catalysts can result in Si–Si bond scission. In this work, we demonstrate borane-catalyzed hydrosilylation reactions between α-olefins and small molecules or three distinct poly(cyclosilane) architectures. We investigate chemoselectivity for end group versus internal Si–H groups and find that ²⁹Si cross-polarization magic angle spinning can provide insight on site-selectivity in the functionalization of a complex poly(cyclosilane). Furthermore, we show that postpolymerization hydrosilylation, converting oxidatively sensitive Si–H groups to Si–alkyl chains, modulates solubility and physical characteristics, optical properties, pyrolytic reactivity, and air sensitivity.

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Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0020681

OSTI ID:: 2338167

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 9 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
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