Hyperbranched polymers have been widely used in various fields because of their special architecture, such as random branched topology, high functional group density, three-dimensional porous structure, which offers them with new properties that linear polymers absent. Therefore, it is very important to develop a new synthetic methodology toward functional hyperbranched polymers. In this work, we have successfully developed the C(sp3)-H activated polymerization of multifunctional internal alkyne and bifunctional secondary amines. Regio- and stereo-regular functional hb-poly(allylic tertiary amine)s (hb-PATAs) with 100% E-isomers and high weight-average molecular weights (Mw up to 27000) were obtained in satisfactory yields (up to 82%). The hb-PATAs possess excellent solubility, thermal stability, and film-forming property. And the polymer films show high refractive index (n632.8nm = 1.77) , small dispersion constant and good photoluminescence quantum yield (43.7%) . Moreover, the hb-PATAs containing TPE moiety displays unique aggregation-enhanced emission (AEE) property and can be used for explosive detection with a superamplification quenching effect. In addition, thanks to the propypargyl groups at the periphery of the hb-PATAs, they can be further modified via another C(sp3)-H activation reaction with alcohols. Thus, this work not only prepared a series of functional luminescent hyperbranched polymers, but also promoted the development of C-H activation in polymer preparation.

C(sp3)-H Polyamination of internal alkynes toward regio- and stereoregular luminescent hb-Poly(allylic tertiary amine)s

ACS Spring 2022

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