Development of ruthenium complexes as dual catalytic systems in simultaneous polymerization ROMP/ATRP

• Grant number: 13/10002-0
• Support Opportunities: Research Grants - Young Investigators Grants
• Start date: December 01, 2013
• End date: November 30, 2017
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
• Principal Investigator: Valdemiro Pereira de Carvalho Júnior
• Grantee: Valdemiro Pereira de Carvalho Júnior
• Host Institution: Faculdade de Ciências e Tecnologia (FCT). Universidade Estadual Paulista (UNESP). Campus de Presidente Prudente. Presidente Prudente , SP, Brazil
• Associated scholarship(s): 15/01165-9 - Ruthenium complexes bearing N-heterocyclic carbene and dimethylsulphoxide as dual catalyts in simultaneous polymerization ROMP/ATRP, BP.IC

Abstract

New ruthenium complexes will be developed to promote the ring opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP) simultaneously. The proposal is to systematically evaluate different combinations of ancillary ligands in the coordination sphere of ruthenium complexes and then, reach a fine tuning through the variation of the electronic and steric contributions, which have the task of driving the reactivity of these complexes to operate efficiently in the tandem catalysis ROMP/ATRP. The investigated ligands will be different carbenes and sulfoxides simultaneously coordinated to the ruthenium center to polymerize cyclic olefin monomers via ROMP and vinyl monomer via ATRP in order to obtain block copolymers composed of mechanically incompatible monomers. Initially, the research will focus on the catalytic activity of the complexes in ROMP and ATRP reactions separately, considering that a wide understanding of individual reactions will be a key step towards to the development of dual catalysts for tandem catalysis ROMP/ATRP. The intension is to provide base for understanding the performance of the catalysts, as well as the formation of reaction intermediates involved in each catalyse, and then, design catalytic systems that combine reactivity and selectivity for synthesis of new materials with different architecture by tandem polymerization ROMP/ATRP. (AU)

Scientific publications

(11)

(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)

ALVES AFONSO, MARIA BEATRIZ; GONCALVES, LUCAS GOMES; SILVA, TALITA TEIXEIRA; SILVA SA, JOSE LUIZ; BATISTA, NOUGA CARDOSO; GOI, BEATRIZ ELEUTERIO; CARVALHO JUNIOR, VALDEMIRO PEREIRA. Synthesis of poly(ethyl methacrylate-co-methyl methacrylate) obtained via ATRP using ruthenium benzylidene complexes. POLIMEROS-CIENCIA E TECNOLOGIA, v. 28, n. 3, p. 220-225, JUL-SEP 2018. (13/10002-0)

SILVA, RODOLPHO A. N.; BORIM, PATRICIA; FONSECA, LARISSA R.; LIMA-NETO, BENEDITO S.; SILVA SA, JOSE L.; CARVALHO-, JR., VALDEMIRO P.. Non-carbene Complex [RuCl2(PPh3)(2)(azocane)] as Active Catalyst Precursor for ROMP and ATRP. CATALYSIS LETTERS, v. 147, n. 5, p. 1144-1152, MAY 2017. (11/12571-7, 13/10002-0)

CRUZ, THAIS R.; SILVA, RODOLPHO A. N.; MACHADO, ANTONIO E. H.; LIMA-NETO, BENEDITO S.; GOI, BEATRIZ E.; CARVALHO, JR., VALDEMIRO P.. New dmso-ruthenium catalysts bearing N-heterocyclic carbene ligands for the ring-opening metathesis of norbornene. NEW JOURNAL OF CHEMISTRY, v. 43, n. 16, p. 6220-6227, APR 28 2019. (13/10002-0)

CRUZ, THAIS R.; BORIM, PATRICIA; GOI, BEATRIZ E.; SILVA SA, JOSE L.; LIMA-NETO, BENEDITO S.; CARVALHO, JR., VALDEMIRO P.. Atom transfer radical polymerization by [RuCl2(PPh3)(2)(amine)] catalysts: Cyclic amines as tuner of reactivity. JOURNAL OF POLYMER RESEARCH, v. 24, n. 11, OCT 28 2017. (13/10002-0)

AFONSO, MARIA BEATRIZ A.; CRUZ, THAIS R.; SILVA, YAN F.; PEREIRA, JOAO CLECIO A.; MACHADO, ANTONIO E. H.; GOI, BEATRIZ E.; LIMA-NETO, BENEDITO S.; CARVALHO-, JR., VALDEMIRO P.. Ruthenium(II) complexes of Schiff base derived from cycloalkylamines as pre-catalysts for ROMP of norbornene and ATRP of methyl methacrylate. JOURNAL OF ORGANOMETALLIC CHEMISTRY, v. 851, p. 225-234, NOV 15 2017. (13/10002-0)

ALVES AFONSO, MARIA BEATRIZ; GONCALVES, LUCAS GOMES; SILVA, TALITA TEIXEIRA; SILVA SA, JOSE LUIZ; BATISTA, NOUGA CARDOSO; GOI, BEATRIZ ELEUTERIO; CARVALHO JUNIOR, VALDEMIRO PEREIRA. Synthesis of poly(ethyl methacrylate-co-methyl methacrylate) obtained via ATRP using ruthenium benzylidene complexes. POLIMEROS-CIENCIA E TECNOLOGIA, v. 28, n. 3, p. 6-pg., 2018-07-01. (13/10002-0)

SILVA, TALITA T.; SILVA, YAN F.; MACHADO, ANTONIO E. H.; MAIA, PEDRO IVO S.; TASSO, CARLOS R. B.; LIMA-NETO, BENEDITO S.; SILVA SA, JOSE L.; CARVALHO-JR, VALDEMIRO P.; BATISTA, NOUGA C.; GOI, BEATRIZ E.. Cycloalkyl-substituted salicylaldimine-nickel(II) complexes as mediators in controlled radical polymerization of vinyl acetate. Journal of Macromolecular Science Part A-Pure and Applied Chemistry, v. 56, n. 12, p. 1132-1140, DEC 2 2019. (13/11883-0, 13/10002-0)

SILVA, YAN F.; RIGA, BEATRIZ A.; DEFLON, VICTOR M.; SOUZA, JHONATHAN R.; SILVA, LEONARDO H. F.; MACHADO, ANTONIO E. H.; MAIA, PEDRO IVO S.; CARVALHO-JR VALDEMIRO, P.; GOI, BEATRIZ E.. Organometallic-mediated radical polymerization using well-defined Schiff base cobalt(II) complexes. Journal of Coordination Chemistry, v. 71, n. 22, p. 3776-3789, NOV 17 2018. (13/11883-0, 13/10002-0)

IDEHARA, ANDRE H. S.; GOIS, PATRIK D. S.; FERNANDEZ, HENRIQUE; GOI, BEATRIZ E.; MACHADO, ANTONIO E. H.; LIMA-NETO, BENEDITO S.; CARVALHO, JR., VALDEMIRO P.. Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands. MOLECULAR CATALYSIS, v. 448, p. 135-143, APR 2018. (13/10002-0)

MARIA BEATRIZ A. AFONSO; LUCAS G. GONÇALVES; PATRÍCIA BORIM; JOSÉ LUIZ S. SÁ; BEATRIZ E. GOI; VALDEMIRO P. CARVALHO-JR.. Atom Transfer Radical Polymerization of Methyl Methacrylate Mediated by Grubbs 1st and 2nd Generation Catalysts: Insight into the Active Species. Journal of the Brazilian Chemical Society, v. 28, n. 8, p. 1407-1413, 2017-08-00. (13/10002-0)

BORIM, PATRICIA; LIMA-NETO, BENEDITO S.; GOI, BEATRIZ E.; CARVALHO, JR., VALDEMIRO P.. Ru-dimethyl sulfoxide complexes as catalysts precursors for ROMP of norbornene and ATRP of methyl methacrylate. Inorganica Chimica Acta, v. 456, p. 171-178, FEB 24 2017. (13/10002-0)