Aliphatic polyketones via cross-metathesis polymerization: Synthesis and post-polymerization modification. (17th December 2019)

• Record Type: Journal Article
• Authors: Zeng, Fu-Rong; Xu, Jing; Xiong, Qi; Qin, Kai-Xuan; Xu, Wei-Jun; Wang, Yue-Xin; Liu, Zan-Jiao; Li, Zi-Long; Li, Zi-Chen
• Is Part Of: Polymer. Volume 185(2019)
• Publication Date: 2019-12-17
• Subjects: Aliphatic polyketones -- Cross-metathesis polymerization -- Thiol-Michael chemistry; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; 547.7
• DOI: 10.1016/j.polymer.2019.121936
• Languages: English
• ISSNs: 0032-3861

Abstract

Abstract: Polyolefins attract considerable attention due to their vast consumption and wide application. In this study, cross-metathesis polymerization (CMP) is demonstrated to be an efficient and feasible method for the synthesis of aliphatic polyketones. The synthetic route features good yield, mild condition and easy operation. The success of CMP relies on the high cross-metathesis tendency between α -olefin and vinyl ketone units of monomer 2 . Optimization of polymerization condition was conducted to generate unsaturated polyketone P0 ( M n, GPC = 14 kDa), and the results of kinetic study verified high efficiency and structural integrity of this system. Furthermore, post-polymerization modification of P0 by using thiol-Michael chemistry furnished functional polyketones P1 –P6, and full conversion of the internal vinyl ketone groups of P0 was observed in each case. The pristine and functional polyketones P0 –P6 were virtually soluble in most common organic solvents. In particular, hydrophobic and fluorescent polyketones (P5 and P6 ) were also obtained by this means. Therefore, this synthetic strategy shows promising future and exemplifies huge potential for the synthesis of a diverse range of functional polyketones. Graphical abstract: Image 1 Highlights: Cross-metathesis polymerization proves to be an efficient and straightforward method for the synthesis of unsaturated polyketone. Post-polymerization modification of pristine polyketone enables the generation of a diverse range of functional polymeric materials. Full conversion of the internal alkene units of unsaturated polyketone is realized by using thiol-Michael chemistry. A natural product derivative, 10-undecenal, is selected as the starting material for concise synthesis of bio-based monomer. Characterization of polyketones can be routinely conducted due to their solubility in most common organic solvents.