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Poly(cyclosilane) Postpolymerization Hydrosilylation
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DOI：10.1021/acs.macromol.3c02110.png)
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摘要
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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. Herein, we demonstrate borane-catalyzed hydrosilylation reactions between alpha-olefins and small molecules or three distinct poly(cyclosilane) architectures. We investigate chemoselectivity for end group versus internal Si-H groups and find that Si-29 cross-polarization magic angle spinning can provide insight on site-selectivity in the functionalization of a complex poly(cyclosilane). We further 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.
Keyword:
NMR-SPECTROSCOPY
SILICON
POLYSILANES
SILANES
MICROSTRUCTURE
CONFIGURATION
OLIGOSILANES
POLYMERS
期刊
IF:
5.2
论文数:
3.7W
被引数:
9.4W
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