Control over the relative reactivities of monomers in RAFT copolymerization of styrene and acrylic acid

E V Chernikova; S D Zaitsev; A V Plutalova; K O Mineeva; O S Zotova; D V Vishnevetsky

doi:10.1039/c8ra00048d

Control over the relative reactivities of monomers in RAFT copolymerization of styrene and acrylic acid

RSC Adv. 2018 Apr 18;8(26):14300-14310. doi: 10.1039/c8ra00048d. eCollection 2018 Apr 17.

Authors

E V Chernikova¹, S D Zaitsev², A V Plutalova¹, K O Mineeva¹, O S Zotova², D V Vishnevetsky^{1

3}

Affiliations

¹ Polymer Department, Faculty of Chemistry, Lomonosov Moscow State University Lenin Hills, 1, bld.3 Moscow 119991 Russian Federation chernikova_elena@mail.ru.
² Nizhni Novgorod State University pr. Gagarina, 23 Nizhni Novgorod 603950 Russian Federation szay@inbox.ru.
³ Tver State University Zhelyabova st., 33 Tver 170100 Russian Federation.

Abstract

The relative monomer reactivities in the reversible addition-fragmentation chain transfer (RAFT) radical copolymerization of styrene (S) and acrylic acid (AA) in a solution of the polar solvent N,N-dimethylformamide are found to be dependent on the chemical nature of the RAFT agent. Polymeric RAFT agents based on polyacrylic acid enhance the difference in monomer reactivities (dithiobenzoate - r _AA = 0.09 ± 0.02, r _S = 3.5 ± 1.2, trithiocarbonate - r _AA = 0.08 ± 0.04, r _S = 3.03 ± 1.78) compared to low molecular weight RAFT agents (dibenzyl dithiobenzoate - r _AA = 0.14 ± 0.01, r _S = 1.00 ± 0.01, dibenzyl trithiocarbonate - r _AA = 0.08 ± 0.01, r _S = 0.85 ± 0.03). The opposite effect on the relative reactivity of acrylic acid is observed when polymeric RAFT agents based on polystyrene are used (dithiobenzoate - r _AA = 3.3 ± 0.4, r _S = 0.72 ± 0.05, trithiocarbonate - r _AA = 0.11 ± 0.01, r _S = 0.54 ± 0.03). In all the investigated systems the copolymers formed are characterized by narrow MWD due to the high efficiency of the chosen RAFT agents.