Upscaling single unit monomer insertion to synthesize discrete oligomers. Issue 18 (30th January 2019)

• Record Type: Journal Article
• Authors: Huang, Zixuan; Corrigan, Nathaniel; Lin, Shiyang; Boyer, Cyrille; Xu, Jiangtao
• Is Part Of: Journal of polymer science. Volume 57:Issue 18(2019)
• Page Start: 1947
• Page End: 1955
• Publication Date: 2019-01-30
• Subjects: catalysis -- discrete oligomers -- flow reaction -- oligomers -- oxygen tolerance -- PET‐RAFT polymerization -- reversible addition‐fragmentation chain transfer (RAFT) -- single unit monomer insertion; 547
• DOI: 10.1002/pola.29330
• Languages: English
• ISSNs: 0887-624X

Abstract

ABSTRACT: As one of the emerging techniques for preparing discrete oligomers, the photo‐RAFT single unit monomer insertion (SUMI) process has shown its uniqueness and superiority in the control of both monomer sequence and stereochemistry. However, current precision polymer synthesis techniques are still burdened by the scalability challenges, such as low reaction yields, small product quantities, and long production times. Herein, we successfully established a practical protocol to address scalability problems in the photo‐RAFT SUMI processes. A series of discrete oligomers containing up to five monomer units were synthesized in batch and flow reactors by sequential and alternating SUMI of two monomers into a trithiocarbonate RAFT agent under mild reaction conditions and purified by automated flash chromatography. This protocol offers the process with large quantity (grams scale), excellent isolated yields (82%–95% for each step and 59% for five iterations), and short production time (several days for a pentamer). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1947–1955 Abstract : A practical and scalable approach employing successive photo‐RAFT single unit monomer insertion processes was successfully implemented to synthesize discrete oligomers containing up to five monomer units in a handmade flow reactor and an automated purification system with excellent isolated yields (59% for the pentamer).