Issue 48, 2020

Unlocking features of locked-unlocked anionic polymerization

Abstract

Due to unique characteristics of 1-(tri-isopropoxymethylsilylphenyl)-1phenylethylene (DPE-Si(OiPr)3), quantitative locked (the living species became dormant for endcapping with DPE-Si(OiPr)3) and unlocked (the dormant species regained the activity after adding the alkali metal alkoxides) anionic polymerization has been realized. In this work, the features of locked-unlocked anionic polymerization were carefully investigated with sequential feeding strategies. By combining the results from SEC, 1H-NMR, MALDI-TOF-MS and DFT calculations, the main features of this mechanism were revealed as follows: (1) it is a kinetically controlled process (kDS and kSS) due to the inherent features of different living species. Comparable initiation and propagation rates are required to ensure the simultaneous chain growth from unlocked living species; (2) the transformation between locked and unlocked species depends on the alkalinity of the alkali metal alkoxides; the higher the alkalinity, the higher the unlocking efficiency. And promisingly, these findings may contribute to the modulation of molecular weight distribution and facilitate the preparation of position-defined functionalized polymers in the future.

Graphical abstract: Unlocking features of locked-unlocked anionic polymerization

Supplementary files

Article information

Article type
Paper
Submitted
25 Aug 2020
Accepted
17 Nov 2020
First published
18 Nov 2020

Polym. Chem., 2020,11, 7696-7703

Unlocking features of locked-unlocked anionic polymerization

C. Li, X. Leng, L. Han, H. Bai, L. Yang, C. Li, S. Zhang, P. Liu and H. Ma, Polym. Chem., 2020, 11, 7696 DOI: 10.1039/D0PY01202E

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