Selective ring-opening polymerization of glycidyl esters: a versatile synthetic platform for glycerol-based (co)polyethers. Issue 24 (30th May 2022)

• Record Type: Journal Article
• Authors: Liu, Shan; Liu, Lijun; Zhou, Yubo; Chen, Ye; Zhao, Junpeng
• Is Part Of: Polymer chemistry. Volume 13:Issue 24(2022)
• Page Start: 3650
• Page End: 3659
• Publication Date: 2022-05-30
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/d2py00551d
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : Well-defined (isotactic) linear polyglycerols and glycerol-based copolyethers are obtained by controlled and chemoselective ring-opening (co)polymerizations of glycidyl butyrates. Abstract : Linear polyglycerols are highly valued for their excellent hydrophilicity and biocompatibility as well as their multihydroxy nature. We report here a convenient route for the controlled synthesis of polyglycerols through ring-opening polymerization (ROP) of commercialized glycidyl butyrates (GBs). Starting from enantiopure GBs, well-defined poly(glycidyl ester)s with controlled molar mass and stereoregularity are achieved thanks to the chemoselectivity of the bicomponent metal-free catalyst that prevents both transesterification and epimerization. The pendant butyrate groups are readily cleaved by organobase-catalyzed methanolysis, yielding linear polyglycerols that inherit isotacticity and regioregularity from the parent polymers. Copolymerization of S GB and propylene oxide occurs in a random manner resulting in a series of narrowly distributed copolyethers with a precisely regulated number of pendant hydroxyl groups to afford tunable aqueous thermosensitivity. The method is further extended to construct polyglycerol-based amphiphilic and double-hydrophilic copolyethers by block copolymerization of R GB with tert -butyl glycidyl ether and ethylene oxide, respectively.