Toward ultimate control of radical polymerization: functionalized metal–organic frameworks as a robust environment for metal-catalyzed polymerizations

Lee, H.-C., Hwang, J., Schilde, U., Antonietti, M., Matyjaszewski, K. and Schmidt, B. V.K.J. (2018) Toward ultimate control of radical polymerization: functionalized metal–organic frameworks as a robust environment for metal-catalyzed polymerizations. Chemistry of Materials, 30(9), pp. 2983-2994. (doi: 10.1021/acs.chemmater.8b00546)

Abstract

Herein, an approach via combination of confined porous textures and reversible deactivation radical polymerization techniques is proposed to advance synthetic polymer chemistry, i.e., a connection of metal–organic frameworks (MOFs) and activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). Zn2(benzene-1,4-dicarboxylate)2(1,4-diazabicyclo[2.2.2]octane) [Zn2(bdc)2(dabco)] is utilized as a reaction environment for polymerization of various methacrylate monomers (methyl, ethyl, benzyl, and isobornyl methacrylate) in a confined nanochannel, resulting in polymers with control over dispersity, end functionalities, and tacticity with respect to distinct molecular size. To refine and reconsolidate the compartmentation effect on polymer regularity, initiator-functionalized Zn MOF was synthesized via cocrystallization with an initiator-functionalized ligand, 2-(2-bromo-2-methylpropanamido)-1,4-benzenedicarboxylate (Brbdc), in different ratios (10%, 20%, and 50%). Through the embedded initiator, surface-initiated ARGET ATRP was directly initiated from the walls of the nanochannels. The obtained polymers had a high molecular weight up to 392 000. Moreover, a significant improvement in end-group functionality and stereocontrol was observed, entailing polymers with obvious increments in isotacticity. The results highlight a combination of MOFs and ATRP that is a promising and universal methodology to prepare various polymers with high molecular weight exhibiting well-defined uniformity in chain length and microstructure as well as the preserved chain-end functionality.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Schmidt, Dr Bernhard
• Authors: Lee, H.-C., Hwang, J., Schilde, U., Antonietti, M., Matyjaszewski, K., and Schmidt, B. V.K.J.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Chemistry of Materials
• Publisher: American Chemical Society
• ISSN: 0897-4756
• ISSN (Online): 1520-5002
• Published Online: 06 April 2018