Phenol-yne Click Polymerization: An Efficient Technique to Facilely Access Regio- and Stereoregular Poly(vinylene ether ketone)s

5 years ago

Phenol-yne Click Polymerization: An Efficient Technique to Facilely Access Regio- and Stereoregular Poly(vinylene ether ketone)s

Ming Chen, Ben Zhong Tang, Anjun Qin, Wei Bai, Tianwen Bai, Bicheng Yao, Jing Zhi Sun, Yang Shi, Jun Ling, Zhe Wang

Alkyne-based click polymerizations have been well-established. However, in order to expand the family to synthesize polymers with new structures and novel properties, new types of click polymerizations are highly demanded. In this study, for the first time, we established a new efficient and powerful phenol-yne click polymerization. The activated diynes and diphenols could be facilely polymerized in the presence of the Lewis base catalyst of 4-dimethylaminopyridine (DMAP) under mild reaction conditions. Regio- and stereoregular poly(vinylene ether ketone)s (PVEKs) with high molecular weights (up to 35 200) were obtained in excellent yields (up to 99.0 %). The reaction mechanism was well explained under the assistance of density functional theory (DFT) calculation. Furthermore, since the vinyl ether sequence acts as a stable but acid-liable linkage, the polymers could be decomposed under acid conditions, rendering them applicable in biomedical and environmental fields. Cut to the click: The first example of phenol-yne click polymerization was established. Bis(aroylacetylene)s and diphenols could be efficiently polymerized in the presence of organic bases under mild conditions, and regio- and stereoregular polymers with high molecular weights could be produced in excellent yields. An intrinsic mechanism is proposed with the assistance of DFT calculations. The polymers could be completely decomposed when the −lg c(HCl) is lower than 3.2, but are chemical stable above this value.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702966