Desenvolvimento de moléculas bifuncionais a partir de ácidos graxos contendo N-heterocíclicos para formação de complexos de rutênio e de olefinas cíclicas para polimerizações via ROMP
| dc.contributor | Universidade de São Paulo | |
| dc.contributor.author | 1 | |
| dc.date.issued | 2020-07-03 | |
| dc.description.abstract | <span style=\"font-weight: 400;\">Novos ligantes foram sintetizados utilizando 4-aminopiridina (py-4NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">), 3-aminopiridina (py-3NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">) e 1,10-fenantrolina-5-amino (phen-5NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">) como fonte de N-heterocíclicos. Para reagir com o grupo NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> dos N-heterocíclicos foi utilizado como fonte de ácido graxo o óleo de girassol (G) e o ácido oleico (O) comercial. Como fonte de olefina cíclica <span style=\"font-weight: 400;\">o ácido-5-norborneno-2- carboxílico (NBE-COOH). O cloreto de acila formado através de uma reação de acilação reagiu com o grupo NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> para formar os ligantes piridina-3amida ácido graxo girassol (py-3NH-G), piridina-4amida ácido graxo girassol (py-4NH-G), piridina-3amida ácido graxo oleico (py-3NH-O), 1,10-fenantrolina-5amida ácido graxo oleico (phen-5NH-O) e 1,10-fenantrolina-5amida norborneno (phen-5NH-NBE). As purificações foram realizadas através de colunas de sílica gel. Todas as etapas para preparações dos ligantes foram caracterizadas por RMN de <span style=\"font-weight: 400;\">1<span style=\"font-weight: 400;\">H e FTIR. Esses ligantes foram utilizados nas novas sínteses de complexos com rutênio. Os complexos precursores [RuCl<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">].H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O, [RuCl<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(phen)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">].H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O e os complexos [RuCl(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(py-3NH-G)]PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\">(complexo 1), [RuCl(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(py-4NH-G)]PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\"> (complexo 2), [RuCl(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(py-3NH-O)]PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\"> (complexo 3), [Ru(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(py-3NH-O)(py-3NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">)](PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\">)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> (complexo 4), <span style=\"font-weight: 400;\">[Ru(phen)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(phen-5NH-O)](PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\">)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> (complexo 5) e [Ru(phen-5NH-O)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(phen-5NH-NBE)](PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\">)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> (complexo 6) foram sintetizados e caracterizados por RMN de <span style=\"font-weight: 400;\">1<span style=\"font-weight: 400;\">H , FTIR, voltametria cíclica e espectrofotometria UV-Vis. Nas purificações dos complexos derivados do precursor [RuCl<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">].H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O foram necessários o uso da coluna de sílica gel. Os complexos 1, 2, 3 e 4 foram irradiados em solução de acetonitrila e os novos ligantes sintetizados nesse trabalho foram substituídos. Com o complexo 6 e norborneno foi possível formar o polinorborneno com o metalomonômero ligado à cadeia. Esse polímero foi caracterizado por espectrofotometria UV-Vis, fluorimetria, GPC e TGA. <span style=\"font-weight: 400;\">Obteve-se M<span style=\"font-weight: 400;\">w<span style=\"font-weight: 400;\"> = 3,7x10<span style=\"font-weight: 400;\">5<span style=\"font-weight: 400;\"> g/mol e IPD = 2,3 ± 0,2, com estabilidade térmica até 250 °C<span style=\"font-weight: 400;\">. O polímero manteve as características físicas e químicas do polinorborneno e do metalomonômero. | |
| dc.description.abstract | <span style=\"font-weight: 400;\">New ligands have been synthesized using 4-aminopyridine (py-4NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">), 3-aminopyridine (py-3NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">) and 1,10-phenanthroline-5-amino (phen-5NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">) as a source of N-heterocyclics. To react with the NH<span style=\"font-weight: 400;\">2 <span style=\"font-weight: 400;\">group of N-heterocyclics, sunflower (G) and oleic (O) oils were used as fatty acid sources and 5-norbornene-2-carboxylic acid (NBE-COOH) as a source of cyclic olefin. The acylchloride formed through an acylation reaction reacted with the NH<span style=\"font-weight: 400;\">2 <span style=\"font-weight: 400;\">group to form the sunflower fatty acid (py-3NH-G), pyridine-4amide sunflower fatty acid (py-4NH-G), pyridine- 3amide oleic fatty acid (py-3NH-O), 1,10-phenanthroline-5amide oleic fatty acid (phen-5NH-O) and 1,10-phenanthroline-5amide norbornene (phen-5NH-NBE). Purifications were performed using silica gel columns. All steps for preparing the ligands were characterized by <span style=\"font-weight: 400;\">1<span style=\"font-weight: 400;\">H NMR and FTIR. These ligands were used in the new synthesis of complexes with ruthenium. The precursor complexes [RuCl<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">].H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O, [RuCl<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(phen)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">].H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O and the complexes [RuCl(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(py-3NH-G)]PF<span style=\"font-weight: 400;\">6 <span style=\"font-weight: 400;\">(complex 1), [RuCl(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(py-4NH-G)]PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\"> (complex 2), [RuCl(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(Py-3NH-O)]PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\"> (complex 3), [Ru(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(py-3NH-O)(py-3NH<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">)](PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\">)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> (complex 4), [Ru(phen)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(phen-5NH-O)](PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\">)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> (complex 5) and [Ru(phen-5NH-O)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(phen-5NH-NBE)](PF<span style=\"font-weight: 400;\">6<span style=\"font-weight: 400;\">)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> (complex 6) were synthesized and characterized by 1H NMR, FTIR, cyclic voltammetry and UV-Vis spectrophotometry. In the purifications of the complexes derived from the precursor [RuCl<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">(bpy)<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">].H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O, the use of the silica gel column was necessary .Complexes 1, 2, 3 and 4 were irradiated in acetonitrile solution and the new ligands synthesized in this work were replaced. With complex 6 and norbornene, it was possible to form the polynorbornene with the metallomonomer attached to the chain. This polymer was characterized by UV-Vis spectrophotometry, fluorimetry, GPC and TGA. <span style=\"font-weight: 400;\">M<span style=\"font-weight: 400;\">w<span style=\"font-weight: 400;\"> = 3.7x10<span style=\"font-weight: 400;\">5<span style=\"font-weight: 400;\"> g /mol and IPD = 2.3 ± 0.2 were obtained, with thermal stability up to 250 °C. <span style=\"font-weight: 400;\">The polymer maintained the physical and chemical characteristics of the polynorbornene and the metallomer. | |
| dc.format | application/pdf | |
| dc.identifier.doi | 10.11606/T.75.2020.tde-02072020-143547 | |
| dc.identifier.uri | https://www.teses.usp.br/teses/disponiveis/75/75135/tde-02072020-143547/ | |
| dc.language | pt | |
| dc.rights.holder | 1 | |
| dc.subject | ácidos graxos | |
| dc.subject | moléculas bifuncionais | |
| dc.subject | ROMP | |
| dc.subject | rutênio | |
| dc.subject | bifunctional molecules | |
| dc.subject | fatty acids | |
| dc.subject | ROMP | |
| dc.subject | ruthenium | |
| dc.title | Desenvolvimento de moléculas bifuncionais a partir de ácidos graxos contendo N-heterocíclicos para formação de complexos de rutênio e de olefinas cíclicas para polimerizações via ROMP | |
| dc.title.alternative | Development of bifunctional molecules from fatty acids with N-heterocyclics to form ruthenium complexes and cyclic olefins for polymerizations via ROMP | |
| dc.type | Tese de Doutorado | |
| usp.advisor | Lima Neto, Benedito dos Santos | |
| usp.date.defense | 2020-03-10 |