From Impossible to Possible: Atom‐Economic Polymerization of Low Strain Five‐Membered Carbonates. Issue 5 (14th December 2021)

• Record Type: Journal Article
• Authors: You, Huai; Wang, Enhao; Cao, Han; Zhuo, Chunwei; Liu, Shunjie; Wang, Xianhong; Wang, Fosong
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 5(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-12-14
• Subjects: Atom-economic polymerization -- Propylene carbonate -- Ring-opening alternating copolymerization (ROAC) -- Slow-release -- Tandem polymerizations; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202113152
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The direct ring‐opening polymerization (ROP) of propylene carbonate (PC) only affords oligomers with substantial unidentified by‐products, which hinders the efficient utilization of PC. Through detailed studies, for the first time, a careful mechanism involving the in situ release of propylene oxide (PO) from PC decarboxylation is proposed. Further, we report a novel strategy of copolymerization of PC/cyclic anhydrides via in situ capture of the formed intermediates. Results show that PC is successfully transformed into polyesters. Especially for the ring‐opening alternating copolymerization (ROAC) of PC/phthalic anhydride (PA), a variety of advantages are manifold: i) slow‐release of PO ensuring a perfectly alternating structure; ii) quantitative and fast transformation of PC; iii) visualization of polymerization process by a CO2 pressure gauge. Of importance, through tandem polymerizations, PC is fully transformed into polyesters and polycarbonates concurrently, thus achieving PC utilization with a high atom‐economy. Abstract : An atom‐economic polymerization of five‐membered propylene carbonate (PC) for preparation of polyester and polycarbonate simultaneously is reported. The key premise of our strategy is the careful elaboration of the mechanism of direct ring‐opening polymerization of PC, which emphasizes the importance of the in situ released propylene oxide.