An efficient, atom-economic, oxygen-tolerant, and water-tolerant strategy has been established to synthesize cyano-rich polyesters. Four kinds of organic bases, 1,1,3,3-tetramethylguanidine (TMG), 4-dimethylaminopyridine, triethylamine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were explored for accelerating Michael addition polymerization of malononitrile and 1,4-butandiol diacrylate. TMG can promote the polymerization efficiently under mild conditions to quantitatively afford polyester with high-molecular weight and moderate polydispersity. The comparison of the kinetic studies of
In this work, we report the synthesis and polymerization performances of terpenoid-derived camphoric anhydride (CA). Utilizing simple organo-base t BuP 2 as the catalyst, CA can polymerize with various epoxides by efficient and controlled ring-opening alternating copolymerization (ROAC) to afford perfectly alternating poly(CA-alt-epoxide). Kinetic study shows that the polymerization proceeds following zero-order dependence on the concentration of CA. The selfswitchable terpolymerization from the mixture of CA, propylene oxide (PO) and ε-caprolactone (CL) is conducted under the catalysis of t BuP 2 . First, ROAC of CA and PO is carried out exclusively with benzyl alcohol as initiator. Then, block copolymer (BCP) poly(CA-alt-PO)-b-PCL is obtained via the sequential polymerizations after the complete consumption of CA. The followed ringopening polymerization (ROP) of CL is initiated by the terminal hydroxyl of the ROAC-resulted poly(CA-alt-PO) polyester without external stimulus. During the process, the excess PO compound remains intact. The one-pot synthesis displays distinct living nature and perfect chemoselectivity. The as-prepared terpenoidderived alternating and BCP's exhibit elevated thermal properties.
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