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

Autor(es)

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]

Afiliação do(s) autor(es)

^[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

• Tipo de documento: Artigo Científico
• Fonte: EUROPEAN POLYMER JOURNAL; v. 159, OCT 5 2021.
• Citações Web of Science: 0

Resumo

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)

• Processo FAPESP: 18/06340-1 - Complexos bimetálicos de rutênio(II) e níquel(II): acoplamento de reações mecanisticamente incompatíveis usando catalisadores multifuncionais via catálise tandem
• Beneficiário: Valdemiro Pereira de Carvalho Júnior
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 19/03354-4 - Novos complexos organometálicos Co(III) coordenados a bases de schiff assimétricas para mediar a foto-OMRP
• Beneficiário: Larissa Fazioni de Oliveira
• Modalidade de apoio: Bolsas no Brasil - Mestrado
• Processo FAPESP: 18/19395-9 - Síntese de novos complexos organometálicos de Fe(III), Co(III) e Ni(III) coordenados a bases de Schiff assimétricas para mediar a foto-OMRP
• Beneficiário: Beatriz Eleutério Goi Carvalho
• Modalidade de apoio: Auxílio à Pesquisa - Regular