Issue 24, 2023

Alkylborane initiated RAFT polymerization: impact of carboxylic acid deblockers

Abstract

In this report, we explore the role of carboxylic acid deblockers in an oxygen tolerant, room temperature, and alkylborane initiated reversible addition–fragmentation chain transfer (AI-RAFT) polymerization. Our studies employ an air-stable and coordinated trialkylborane–amine complex as the initiator which upon exposure to deblocker liberates free alkylborane that consumes oxygen and generates radicals to drive RAFT polymerization. Kinetic experiments reveal an enhancement in the polymerization rate when using higher concentrations of propionic acid deblocker and that the carboxylic acid has a partial order of one, aligning with the homolytic substitution mechanism for the autoxidation of alkylboranes. Different carboxylic acid deblockers were also investigated by their relative pKa values, showing that lower pKa acids can be employed at greatly diminished concentrations while still providing high monomer conversions, predetermined molecular weights, and narrow dispersity polymers. The findings disclosed in this report provide important kinetic parameters, mechanistic insights, and formulation details which are instrumental in understanding and improving AI-RAFT.

Graphical abstract: Alkylborane initiated RAFT polymerization: impact of carboxylic acid deblockers

Supplementary files

Article information

Article type
Paper
Submitted
29 mar 2023
Accepted
19 máj 2023
First published
01 jún 2023

Polym. Chem., 2023,14, 2872-2877

Alkylborane initiated RAFT polymerization: impact of carboxylic acid deblockers

O. R. Wilson and A. J. D. Magenau, Polym. Chem., 2023, 14, 2872 DOI: 10.1039/D3PY00348E

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