Ethynylsulfone-Based Spontaneous Amino-yne Click Polymerization: A Facile Tool toward Regio- and Stereoregular Dynamic Polymers

• Published in: Macromolecules 2019-06, Vol.52 (12), p.4526-4533
• Main Authors: Chen, Xuemei, Hu, Rong, Qi, Chunxuan, Fu, Xinyao, Wang, Jia, He, Benzhao, Huang, Die, Qin, Anjun, Tang, Ben Zhong
• Format: Article
• Language: English
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/acs.macromol.9b00670

Development of efficient polymerizations is crucial for polymer science from which polymeric materials with versatile properties could be produced. In this work, a new and efficient spontaneous amino-yne click polymerization is successfully established by using activated diynes of bis­(ethynylsulfone)­s. Compared with the ester-activated diynes, that is, dipropiolates, bis­(ethynylsulfone)­s could polymerize with all kinds of diamines including aliphatic and aromatic primary and secondary ones under very mild reaction conditions, and soluble and thermally stable poly­(β-aminovinylsulfone)­s (PAVSs) with high weight-average molecular weights (M w up to 160,000) and excellent regio- and stereoregularity (the ratio of E isomers up to 100%) were obtained in high yields (up to 99%). Due to the strong electron-withdrawing ability of sulfonyl groups, the resultant PAVSs show a dynamic property and could undergo the amine exchange, which makes the polymers readily degrade upon addition of monoamines. Moreover, this highly efficient spontaneous amino-yne click reaction could be used to facilely label and decorate proteins. Thus, this work not only establishes a more efficient amino-yne click polymerization, which could be used to label bioconjugates, but also provides a novel strategy to construct regio- and stereoregular dynamic polymers.