TY  - JOUR
A1  - Lee, Hui-Chun
A1  - Hwang, Jongkook
A1  - Schilde, Uwe
A1  - Antonietti, Markus
A1  - Matyjaszewski, Krzysztof
A1  - Schmidt, Bernhard V. K. J.
T1  - Toward ultimate control of radical polymerization
T2  - Chemistry of materials : a publication of the American Chemical Society
N2  - 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). Zn-2(benzene-1,4-dicarboxylate)2(1,4-diazabicyclo[2.2.2]-octane) [Zn-2(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.
Y1  - 2018
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/52910
SN  - 0897-4756
SN  - 1520-5002
VL  - 30
IS  - 9
SP  - 2983
EP  - 2994
PB  - American Chemical Society
CY  - Washington
ER  -