Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones

Highly potent ionic organocatalyst is developed for room-temperature controlled ring-opening polymerization(ROP)of lactones,includingδ-valerolactone,ε-caprolactone,andδ-hexalactone.The catalysts are prepared by simply mixing tetra-n-butyl ammonium hydroxide and a(thio)urea at elevated temperature under vacuum,and used in cooperation with an alcoholic initiator.The performance of the catalyst is readily adjusted and optimized through variation of the(thio)urea precursor,catalyst composition,and reaction condition.Urea-derived catalysts are generally superior to thiourea-derived ones.Provided with proper N-substituents,the catalyst affords both high polymerization efficiency and high selectivity for monomer enchainment over macromolecular transesterification,even at high monomer conversion and/or substantially extended reaction time.In addition to acidity,structural symmetry of the urea also proves decisive for the catalytic activity,which enables a catalyst-assisted proton transfer process for the ring-opening of lactone and thus provides a novel mechanistic insight for ROP catalyzed by hydrogen-bonding type bifunctional ionic organocatalysts.

Amine-Actuated Catalyst Switch for One-Pot Synthesis of Ether-Ester Type Block Copolymers

Organocatalysis has shown special potency for simplifying the construction of complex polymer structures.We are reporting here a one-pot synthetic pathway using amine as a selectivity-switching agent in the two-component catalytic system consisting of triethylborane(Et_(3)B)and a phosphazene base.We first modelled the interactions of a variety of amines with Et_(3)B by density functional theory calculations.The results indicate that the aliphatic diamines comprising both primary and tertiary amino groups,capable of forming stable intramolecular hydrogen bonds,undergo the strongest complexation with Et_(3)B.Accordingly,experimental results demonstrate that the addition of such amines promptly actuates the in situ selectivity switch from Lewis pair-catalyzed ring-opening polymerization(ROP)of epoxide(propylene oxide,n-butylglycidyl ether,or glycidyl phenyl ether)to organobase-catalyzed ROP ofδ-valerolactone,allowing one-pot continuous synthesis of ether-ester type block copolymers.We thus exploited the noncovalent interaction between amine and Et_(3)B to refine the catalyst switch strategy by exempting it from loading of extra catalyst.