Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type Co-II complexes

Author(s)

Oliveira, Larissa F. ^[1] ; Bignardi, Camila ^[1] ; Pesqueira, Naralyne M. ^[1] ; Riga-Rocha, Beatriz A. ^[1] ; Machado, Antonio E. H. ^[2] ; Carvalho-Jr, Valdemiro P. ; Goi, Beatriz E. ^[3]

Affiliation

^[1] UNESP Univ Estadual Paulista, Fac Ciencias & Tecnol, BR-19060900 Presidente Prudente, SP - Brazil

^[2] Univ Fed Uberlandia, Inst Quim, POB 593, BR-38400089 Uberlandia, MG - Brazil

^[3] Carvalho-Jr, Jr., Valdemiro P., UNESP Univ Estadual Paulista, Fac Ciencias & Tecnol, BR-19060900 Presidente Prudente, SP - Brazil

• Document type: Journal article
• Source: EUROPEAN POLYMER JOURNAL; v. 159, OCT 5 2021.
• Web of Science Citations: 0

Abstract

In this study, we synthesized the complex {[}Co(BuSalen)] using the novel tetradentate BuSalen ligand and analyzed its ability as a controlling agent for the photo-induced organometallic-mediated radical polymerization (photo-OMRP) of butyl acrylate (BA) using diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as photo initiator. BA polymerization with {[}Co(BuSalen)] reached significant control levels using the {[}BA]/{[}Co-II]/TPO molar ratio of 600/1/1. The {[}Co(Salen)] and {[}Co(Bu(2)Salen)] complexes were also obtained following literature methods aiming a comparison in the mediating ability in photo-OMRP. {[}Co(BuSalen)] and {[}Co(Bu(2)Salen)] showed better controlling ability, as observed in the copolymerization study (D= 2.64, 1.50, and 1.26 for complexes {[}Co(Salen)], {[}Co(BuSalen)] and {[}Co(Bu(2)Salen)], respectively). Kinetics studies and computational investigations support a reversible termination (RT) mechanism and a tailorable Co-II complex reactivity mainly altered by Schiff-base steric factors. Calculated thermodynamic parameters agree with the controlling degree delivered by these complexes, since the polymerization control increases with increasing the Delta G values for the formation of dormant species. (AU)

• FAPESP's process: 18/06340-1 - Bimetallic complexes of ruthenium(II) and nickel(II): coupling of mechanistically-incompatible reactions using multifunctional catalysts via tandem catalysis
• Grantee: Valdemiro Pereira de Carvalho Júnior
• Support Opportunities: Regular Research Grants
• FAPESP's process: 19/03354-4 - New organometallic complexes Co (III) coordinated to asymmetric schiff bases to mediate photo-OMRP
• Grantee: Larissa Fazioni de Oliveira
• Support Opportunities: Scholarships in Brazil - Master
• FAPESP's process: 18/19395-9 - Synthesis of new organometallic complexes of Fe (III), Co (III) and Ni (III) coordinated to asymmetric Schiff bases to mediate photo-OMRP
• Grantee: Beatriz Eleutério Goi Carvalho
• Support Opportunities: Regular Research Grants