Sustainable chemistry based on olefin metathesis: development of olefins from bio-molecules via economically viable catalysts.

• Grant number: 23/17102-2
• Support Opportunities: Regular Research Grants
• Start date: December 01, 2024
• End date: November 30, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
• Principal Investigator: Benedito dos Santos Lima Neto
• Grantee: Benedito dos Santos Lima Neto
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil

Abstract

This project deals with sustainable chemistry based on olefin metathesis, which aims to develop materials from bio-substituted and/or eco-substituted monomers. To this end, bio-substituted and eco-substituted norbornene (NBE) monomers will be developed for (co)polymerization reactions via ring-opening metathesis (ROMP), with the purpose of using compounds from renewable sources and compounds recovered from chemical recycling. The biosubstituents will be pure commercial saturated and unsaturated fatty acids, or obtained directly from vegetable oils, such as palm, babassu, soybean, canola, linseed, etc. First, NBE-fatty acids of the same molecular composition will be copolymerized with NBE according to the molar ratio to verify the influences of the chain sizes and the number of unsaturations in the fatty acids in the isolated polymers. Thus, it is possible to evaluate how the pendant chains in the different branched polymers are packed and influence the physicochemical, thermal and rheological characteristics. Then, copolymerizations will be performed with percentages of NBE-fatty acids that simulate fatty acid compositions in selected vegetable oils, in order to obtain polymers with NBE-fatty acids obtained from direct reactions with transesterified triglyceride fatty acids. In other procedures, unsaturated fatty acids will be modified by cross-metathesis with molecules of plant origin with unsaturation (jojoba, piperine, estragole, eugenol, methyleugenol, copalic acid, curcumin, cinnamaldehyde, etc.), in order to also generate branched copolymers with differentiated organic chains. Copolymerizations will also be performed with the monomers norbornadiene and diciplopentatadiene to obtain cross-linked polymers, in search of thermosetting polymers. NBE functionalized with chelating amines, s-donor amines and pyridine amines will be obtained for copolymerization with NBE and fatty-NBE, resulting in organic-inorganic hybrid polymers. In this tangent, monomers and polymers connected to MOFs obtained from terephthalic acid (ATF) from chemical recycling of PET bottles will also be developed. One of the purposes is to use compounds recovered from recycled plastics and synthesize ecologically-substituted NBE monomers (NBE-ATF). ATF functionalization with s-donor amines will also be performed, followed by syntheses of hybrid materials. Possible applications of the synthesized polymers and MOFs will be in membranes for separation of small gaseous molecules, capture of dyes and metals in polluted media, formation of materials with luminescent Ru(II) complexes, etc. Ru(II) complexes with different ancillary ligands will be developed to act as catalysts in ROMP reactions, so that stereo-electronic combinations between the ligands promote the reactions. Commercial catalysts will also be used. The proposal is part of the interface between polymeric materials and coordination chemistry. Monomers, copolymers, catalysts and MOFs are designed and then synthesized to obtain materials with specific chemical, physical-chemical, thermal and rheological characteristics. Monitoring of the synthesis and characterization of the resulting compounds will generally be done using spectroscopic, electrochemical, diffraction, thermal and rheological techniques. (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)

AMORIM, KELLY A. E.; MARTINS, VIRGINIA C. A.; LIMA-NETO, BENEDITO S.. Norbornene functionalized with fatty acids: Observing the effect of pendant chains on copolymers obtained by metathesis polymerization. Polymer, v. 317, p. 10-pg., 2024-12-10. (23/17102-2)

CAETANO, RENAN B. G.; SANTIAGO, PEDRO H. O.; ELLENA, JAVIER A.; OLIVEIRA, DANIEL A. S.; BRAGA, ATAUALPA A. C.; LIMA-NETO, BENEDITO S.. Intriguing combinations of p-cymene, chloride ion, phosphines, and amines in ruthenium metal centers: Which ligand decoordinates for ROMP?. MOLECULAR CATALYSIS, v. 569, p. 12-pg., 2024-09-25. (23/17102-2, 17/15850-0, 22/01685-6, 21/10066-5, 15/01491-3)

SILVA, ELIADA A.; SANTIAGO, PEDRO H. O.; ELLENA, JAVIER A.; OLIVEIRA-FILHO, ANTONIO G. S.; DE LIMA BATISTA, ANA PAULA; LIMA-NETO, BENEDITO S.. Reactivity of the p-Cymene-Ruthenium Complex with Two Phenylamines for Metathesis Polymerization of Norbornene Compared to the Reactivity of Complexes with a Single Benzylamine or Dibenzylamine. European Journal of Inorganic Chemistry, v. 27, n. 33, p. 12-pg., 2024-11-21. (17/15850-0, 21/00675-4, 22/12043-5, 23/17102-2, 21/10066-5)

SEABRA, VICTOR; GONCALVES, JOAO M. R.; MOURA, ANA L. S.; LUNA, VINICIUS G.; SANTIAGO, PEDRO H. O.; ELLENA, JAVIER; LIMA-NETO, BENEDITO S.. Facile recovery of terephthalic acid from PET bottles via acid hydrolysis with nitric acid and applications in synthesis of cobalt MOFs. TRANSITION METAL CHEMISTRY, v. N/A, p. 11-pg., 2024-09-16. (17/15850-0, 23/17102-2, 21/10066-5)