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Accessing Unprecedented Polymer Structures by Harnessing Stable α; α-Diboryl Radicals in gem-Diboronate Polymerization
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PRE
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DOI：10.1021/acsmacrolett.6c00225.png)
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Abstract
En 中文
The development of boron-containing polymers as functional materials has been extensively explored through advances in structural design and synthesis. However, the integration of the gem-diboronate motif into polymer backbones remains a significant challenge, with reports on such polymers being scarce. Herein, we report a robust strategy for the synthesis of gem-diboron-based polymers via the radical polymerization of vinyl gem-diboronate monomers, which proceeds through a stable α,α-diboryl radical intermediate. This approach enables the copolymerization of these monomers with a range of conventional comonomers, facilitating the preparation of compositionally diverse copolymers. Notably, the use of maleic anhydride as a comonomer affords well-defined alternating copolymers. The versatility of this platform is underscored by postpolymerization modification, which allows for the transformation of the gem-diboronate units into diverse functional groups. Critically, this methodology provides unprecedented access to copolymers of vinyl alcohol or ethenone (the simplest ketene) with various vinyl monomers, structures that are exceptionally challenging to synthesize through conventional radical polymerization. This platform strategy, with the gem-diboronate unit as a versatile functional handle, enables the precise synthesis of previously inaccessible polymers.
Keywords:
Copolymers
Monomers
Polymers
Radical polymerization
Vinyl