ABC-Type Triblock Copolyacrylamides via Copper-Mediated Reversible Deactivation Radical Polymerization

Fehaid M Alsubaie; Othman Y Alothman; Hassan Fouad; Abdel-Hamid I Mourad

doi:10.3390/polym14010116

ABC-Type Triblock Copolyacrylamides via Copper-Mediated Reversible Deactivation Radical Polymerization

Polymers (Basel). 2021 Dec 29;14(1):116. doi: 10.3390/polym14010116.

Authors

Fehaid M Alsubaie¹, Othman Y Alothman², Hassan Fouad^{3

4}, Abdel-Hamid I Mourad^{5

6

7}

Affiliations

¹ National Center for Chemical Catalysis Technology, King Abdulaziz City for Science and Technology (KACST), P.O. Box 6086, Riyadh 11442, Saudi Arabia.
² Department of Chemical Engineering, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia.
³ Applied Medical Science Department, Community College, King Saud University, P.O. Box 10219, Riyadh 11433, Saudi Arabia.
⁴ Biomedical Engineering Department, Faculty of Engineering, Helwan University, Cairo 11792, Egypt.
⁵ Mechanical and Aerospace Engineering Department, College of Engineering, United Arab Emirate University, Al Ain P.O. Box 15551, United Arab Emirates.
⁶ National Water and Energy Centre, United Arab Emirate University, Al Ain P.O. Box 15551, United Arab Emirates.
⁷ Mechanical Design Department, Faculty of Engineering, Helwan University, Cairo 11795, Egypt.

Abstract

The aqueous Cu(0)-mediated reversible deactivation radical polymerization (RDRP) of triblock copolymers with two block sequences at 0.0 °C is reported herein. Well-defined triblock copolymers initiated from PHEAA or PDMA, containing (A) 2-hydroxyethyl acrylamide (HEAA), (B) N-isopropylacrylamide (NIPAM) and (C) N, N-dimethylacrylamide (DMA), were synthesized. The ultrafast one-pot synthesis of sequence-controlled triblock copolymers via iterative sequential monomer addition after full conversion, without any purification steps throughout the monomer additions, was performed. The narrow dispersities of the triblock copolymers proved the high degree of end-group fidelity of the starting macroinitiator and the absence of any significant undesirable side reactions. Controlled chain length and extremely narrow molecular weight distributions (dispersity ~1.10) were achieved, and quantitative conversion was attained in as little as 52 min. The full disproportionation of CuBr in the presence of Me₆TREN in water prior to both monomer and initiator addition was crucially exploited to produce a well-defined ABC-type triblock copolymer. In addition, the undesirable side reaction that could influence the living nature of the system was investigated. The ability to incorporate several functional monomers without affecting the living nature of the polymerization proves the versatility of this approach.

Keywords: chain extensions; controlled polymerization; dispersity; macroinitiator; radical polymerization; triblock copolyacrylamides; undesirable side reaction.

Grants and funding

RGP-133/King Saud University