Chemoselective Ring‐opening Polymerization of α‐Methylene‐δ‐valerolactone Catalyzed by a Simple Organoaluminum Complex to Prepare Closed‐loop Recyclable Functional Polyester

α‐Methylene‐δ‐valerolactone (MVL) as a bio‐renewable bifunctional monomer has shown great promise to prepare closed‐loop recyclable polyester with pendent functionalizable double bond. However, the chemoselective ring‐opening polymerization (ROP) of MVL still faces challenges including low polymerization temperature, expensive catalyst as well as high catalyst loading. In this contribution, we present the chemoselective and controlled ROP of MVL using a simple organoaluminum complex [MeAl(BHT)2] (BHT = 2,6‐di‐tert‐butyl‐4‐methylphenoxy), which can be easily prepared from commercially available trimethylaluminum and 2,6‐di‐tert‐butyl‐4‐methylphenol without purification. MeAl(BHT)2 exhibits much higher catalytic activity (TOF = 668 h‐1) than that of MeAl[Salen] (TOF = 89 h‐1), a commonly used organoaluminum catalyst. The high chemoselectivity and activity of MeAl(BHT)2 is proposed to originate from the cooperative activation of propagating chain‐ends and monomers via the "coordination‐insertion" mechanism. Remarkably, high‐molecular‐weight P(MVL)ROP can be prepared in bulk using MeAl(BHT)2, which is not accessible by the previous catalysts. This study may advance the development of closed‐loop recyclable polymers considering the easy preparation, low cost and good catalytic performance of MeAl(BHT)2.