Ni(II) complexes for controlled radical photopolymerization reactions (photo-OMRP and CRP2) and application in 3D printing

• Grant number: 21/11741-8
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• Start date: April 01, 2022
• End date: March 31, 2027
• Field of knowledge: Physical Sciences and Mathematics - Chemistry
• Principal Investigator: Beatriz Eleutério Goi Carvalho
• Grantee: Naralyne Martins Pesqueira
• Host Institution: Faculdade de Ciências e Tecnologia (FCT). Universidade Estadual Paulista (UNESP). Campus de Presidente Prudente. Presidente Prudente , SP, Brazil
• Associated scholarship(s): 22/16213-2 - Controlled radical photopolymerization (CRP2) and 3D printing using novel Ni(II) complexes, BE.EP.DD

Abstract

Complexes of NiII metal will be synthesized to catalyze/control Controlled Radical Photopolymerization reactions (photo-OMRP and CRP2). The proposal extends into three stages, which are completely interconnected in the development process. Initially, attention will be directed to the synthesis of Schiff base ligands and non-symmetric NHCs and their respective Ni(II) complexes, involving the entire characterization part through the FTIR, UV-Vis, EPR, 1H and 13C NMR techniques, elemental analysis and mass spectrometry. The second stage will be dedicated to the evaluation of the photochemical properties of the complexes synthesized with Schiff base ligands and with NHCs ligands, considering that they will be used as CRP2 photoinitiator systems. The third step will be dedicated to the evaluation of Ni(II) complexes as photo-OMRP mediators and CRP2 redox photocatalysts using vinyl acetate, methyl acrylate, butyl acrylate and methyl methacrylate monomers. In CRP2, the Ni(II) redox photocatalysts will be studied in the presence of phenacyl bromide and EDB amine under LED irradiation. The copolymerization of selected monomers will also be evaluated using the most efficient photoinitiator systems in the photocontrol of homopolymerization and also the application in 3D printing based on stereolithography. It is intended, therefore, to achieve a fine adjustment of the electronic, electrochemical and steric properties in the coordination sphere of the Ni(II) metal complexes through the combination of ancillary ligands, in order to find the ideal reactivity to promote a satisfactory efficiency in this reaction. (AU)

Scientific publications

(4)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

PESQUEIRA, NARALYNE M.; MORLET-SAVARY, FABRICE; SCHMITT, MICHAEL; JOUAITI, ABDELAZIZ; GOI, BEATRIZ E.; MAURO, MATTEO; LALEVEE, JACQUES. Heteroleptic Copper(I) Complexes with Pyridine-Benzothiazole Ligands as Photocatalysts for Free Radical Photopolymerization and 3D Printing. ACS APPLIED POLYMER MATERIALS, v. N/A, p. 9-pg., 2025-02-06. (21/11873-1, 21/11741-8, 22/16213-2)

PESQUEIRA, NARALYNE M.; BIGNARDI, CAMILA; OLIVEIRA, LARISSA F.; MACHADO, ANTONIO E. H.; CARVALHO-JR, VALDEMIRO P.; GOI, BEATRIZ E.. Visible light-induced radical polymerization of vinyl acetate mediated by organo-nickel N2O2 Schiff-base complexes. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, v. 437, p. 11-pg., 2023-03-01. (18/19395-9, 21/11741-8, 18/06340-1)

PESQUEIRA, NARALYNE M.; MORLET-SAVARY, FABRICE; SCHMITT, MICHAEL; CARVALHO-JR, VALDEMIRO P.; GOI, BEATRIZ E.; LALEVEE, JACQUES. Advancing photopolymerization and 3D printing: High-Performance Ni II complexes bearing N 2 O 2 Schiff-base ligands as photocatalysts. EUROPEAN POLYMER JOURNAL, v. 216, p. 13-pg., 2024-07-03. (21/13128-1, 21/11873-1, 21/11741-8, 22/16213-2)

PESQUEIRA, NARALYNE M.; LIRA, KATHIA H.; BIGNARDI, CAMILA; DA SILVA, MILENE K. C.; SILVA, THIAGO F.; MACHADO, ANTONIO E. H.; NASCIMENTO, OTACIRO R.; CARVALHO-JR, VALDEMIRO P.; GOI, BEATRIZ E.. Photo-induced organo-manganese-mediated radical polymerization of acrylates under LED irradiation. APPLIED ORGANOMETALLIC CHEMISTRY, v. 38, n. 7, p. 14-pg., 2024-04-28. (21/13128-1, 22/16571-6, 21/11741-8, 21/11873-1)