Complexos N?quel-?-diiminas heterogeneizados em MCM-41 e SBA-15: aplica??o em oligomeriza??o de olefinas

• Main Author: Rossetto, En?derson
• Other Authors: 50942611004
• Language: Portuguese
• Published: Universidade Federal do Rio Grande do Norte 2016
• Subjects: CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA; MCM-41; Al-MCM-41; SBA15; Oligomeriza??o; Alquila??o; Etileno; Propileno
• Online Access: http://repositorio.ufrn.br/handle/123456789/20557

Submitted by Automa??o e Estat?stica ([e-mail]) on 2016-05-30T22:35:16Z No. of bitstreams: 1 EnedersonRossetto_TESE.pdf: 3942346 bytes, checksum: 4f772d5bb76c7fedad3ac6471650a54d (MD5) === Approved for entry into archive by Arlan Eloi Leite Silva ([e-mail]) on 2016-06-01T20:17:58Z (GMT) No. of bitstreams: 1 EnedersonRossetto_TESE.pdf: 3942346 bytes, checksum: 4f772d5bb76c7fedad3ac6471650a54d (MD5) === Made available in DSpace on 2016-06-01T20:17:58Z (GMT). No. of bitstreams: 1 EnedersonRossetto_TESE.pdf: 3942346 bytes, checksum: 4f772d5bb76c7fedad3ac6471650a54d (MD5) Previous issue date: 2015-07-31 === Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) === Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) === Os ligantes ?-diiminas 2-(fenil)amino-4-(fenil)imino-2-penteno e o 2-(2,6-dimetilfenil)amino-4-(2,6-dimetilfenil)imino-2-penteno foram combinados com o grupo alcoxisilano cloropropiltrimetoxisilano (CPTMS) e ancorado covalentemente aos suportes mesoporosos MCM-41 e SBA-15, coordenados pela intera??o com os grupos silan?is da matriz das s?licas e complexados com n?quel. Os complexos Ni-?-diimina/mesoporosos foram sintetizados para aplica??o em rea??es de oligomeriza??o do etileno e do propileno e para compara??o dos resultados entre o sistema homog?neo com o sistema heterog?neo. O suporte foi primeiramente sintetizado e calcinado. Ap?s foi realizado o ancoramento dos ligantes e posterior complexac?o do n?quel. Estes materiais foram caracterizados por v?rias t?cnicas, tais como: RMN de 1H, 13C e 29Si, DRX de baixo ?ngulo, Infra-vermelho (IR), an?lise termogravim?trica, an?lise de isotermas de adsor??o-dessor??o de N2, microscopia eletr?nica de transmiss?o (MET) e de varredura (MEV), an?lise elementar e espectroscopia de absor??o at?mica para confirmar o sucesso das s?nteses dos materiais. Ambos os complexos homog?neos e os heterogeneizados s?o ativos e seletivos para as rea??es de oligomeriza??o do etileno e do propileno. Os materiais heterogeneizados foram menos ativos que os complexos an?logos homog?neos nas rea??es de oligomeriza??o do etileno, por?m, foram mais seletivos tanto para fra??es C4 quanto para ?-C4. Nas rea??es com o propileno os complexos homog?neos promoveram ? rea??o de dimeriza??o e os complexos heterogeneizados ? rea??o de alquila??o do tolueno com o propileno. === The ?-diimine ligands 2-(phenyl)amine-4-(phenyl)imine-2-pentene and 2-(2,6- dimethylphenyl)amine-4-(2,6-dimethylphenyl)imine-2-pentene were combined with the alkoxysilane group chloropropyltrimethoxysilane (CPTMS) and covalently anchored to a mesoporous MCM-41, Al-MCM-41 and SBA-15 support, ordered by interaction with the silanols of the silica matrix and complexed with nickel. The complexes were synthesized for application in ethylene and propylene oligomerization and for comparing results between homogeneous and heterogeneous systems. The support is first synthesized, calcined, anchored to the ligand, and then subsequent complexation of nickel is realized. These materials were characterized by several techniques such as 1H, 13C and 29Si NMR, small angle XRD, Infra-red, thermogravimetric analysis, nitrogen adsorption-desorption isotherms, transmission and scanning electron microscopy, elemental analysis, and flame atomic absorption spectroscopy, to confirm the success of the synthesis. Both homogeneous and heterogeneous complexes are active and selective for the reactions of ethylene and propylene oligomerization. The heterogenized materials were less active than the homogeneous analogous complexes in the reactions of oligomerization of ethylene, however, were more selective for both C4 fractions and for ?-C4. In reactions with propylene, the homogeneous complexes promoted the dimerization reaction and the heterogenized complexes the alkylation reaction of toluene with propylene complex.Complexes were tested in recycle reactions proved to be efficient for use in large scale.