Citation: Zhuo-Lun Jiang, Jun-Peng Zhao, Guang-Zhao Zhang. Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones[J]. Chinese Journal of Polymer Science, ;2019, 37(12): 1205-1214. doi: 10.1007/s10118-019-2285-1 shu

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

Faculty of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China

Corresponding author: Jun-Peng Zhao, msjpzhao@scut.edu.cn
Received Date: 26 March 2019
Revised Date: 22 April 2019
Accepted Date: 25 April 2019
Available Online: 26 June 2019

Highly potent ionic organocatalyst is developed for room-temperature controlled ring-opening polymerization (ROP) of lactones, including δ-valerolactone, ε-caprolactone, and δ-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.
- Organocatalytic polymerization,
- Ring-opening polymerization,
- Polyester
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