Immobilization of molecular late transition metal polymerization catalysts on nanomaterials / Zhang, Liping  

Public ISBD Titre : Immobilization of molecular late transition metal polymerization catalysts on nanomaterials Type de document : texte imprimé Auteurs : Zhang, Liping, Auteur ; Durand, Jérôme, Directeur de thèse Année de publication : 2014 Langues : Anglais (eng) Tags : ETHYLENE POLYMERIZATION  ISOPRENE POLYMERIZATION  LATE TRANSITION METAL CATALYST  MULTI-WALLED CARBON NANOTUBES  FEW LAYER GRAPHENE  IRON PARTICLES  PARTICLES SUPPORTED CATALYST  PROTECTIVE ABILITY  NANOCOMPOSITES Résumé : "This present thesis deals with the development of active olefin polymerization catalysts based on late transition metal (nickel and iron) imino-pyridine complexes supported on nanomaterial. Chapter I gives a comprehensive literature review of unsupported and supported ethylene polymerization catalyst. In Chapter II we report the ethylene polymerization studies using nickel complexes containing an –NH2 group for covalent immobilization on multi-walled carbon nanotubes (MWCNTs) of the corresponding precatalysts. Comparison of the homogeneous catalysts with their supported counterparts evidenced higher catalytic activity and higher molecular weights for the polymers produced. In Chapter III, iron complexes containing a pyrene group have been synthesized and immobilized on MWCNTs through non-covalent ?-? interactions between pyrene group and surface of MWCNTs. Activated by MMAO, both the iron complexes and immobilized catalysts show high activities for ethylene polymerization. It was possible to evidence that MWCNTs have a great influence on the catalytic activity and on the structure of the resulting polyethylenes. Imino-pyridine nickel complexes containing various kinds of aromatic groups have been synthesized in Chapter IV and polymerization conditions in the presence and in the absence of nanocarbon materials, such as MWCNTs or few layer graphene (FLG), are discussed. For those nickel catalysts bearing 1-aryliminoethylpyridine ligands, the presence of MWCNTs in the catalytic mixture allows the formation of waxes of lower molecular weight and polydispersity, whereas the presence of FLG proved to be beneficial for the catalytic activity. In Chapter V, isoprene polymerization catalyzed by iron complexes containing polyaromatic groups and non-covalently supported on nanoparticles and confined into the inner cavity of MWCNTs (Cat@NPs and Cat@NPs@MWCNTs) are investigated. Iron complexes show excellent activity for the isoprene polymerization and produced high glass temperature polyisoprene with a high trans-1,4-polyisoprene selectivity. Polymer nanocomposites are produced by supported catalysts and, transmission electron microscopy (TEM) evidenced efficient coating of the resulting polyisoprene around the oxygen sensitive iron nanoparticles." Document : Thèse de Doctorat Etablissement_delivrance : Institut National Polytechnique de Toulouse - INPT Date_soutenance : 24/01/2014 Ecole_doctorale : Sciences de la Matière (université Toulouse III P. Sabatier) Domaine : Chimie/Génie chimique En ligne : http://oatao.univ-toulouse.fr/11748/ Immobilization of molecular late transition metal polymerization catalysts on nanomaterials [texte imprimé] / Zhang, Liping, Auteur ; Durand, Jérôme, Directeur de thèse . - 2014. Langues : Anglais (eng) Tags : ETHYLENE POLYMERIZATION  ISOPRENE POLYMERIZATION  LATE TRANSITION METAL CATALYST  MULTI-WALLED CARBON NANOTUBES  FEW LAYER GRAPHENE  IRON PARTICLES  PARTICLES SUPPORTED CATALYST  PROTECTIVE ABILITY  NANOCOMPOSITES Résumé : "This present thesis deals with the development of active olefin polymerization catalysts based on late transition metal (nickel and iron) imino-pyridine complexes supported on nanomaterial. Chapter I gives a comprehensive literature review of unsupported and supported ethylene polymerization catalyst. In Chapter II we report the ethylene polymerization studies using nickel complexes containing an –NH2 group for covalent immobilization on multi-walled carbon nanotubes (MWCNTs) of the corresponding precatalysts. Comparison of the homogeneous catalysts with their supported counterparts evidenced higher catalytic activity and higher molecular weights for the polymers produced. In Chapter III, iron complexes containing a pyrene group have been synthesized and immobilized on MWCNTs through non-covalent ?-? interactions between pyrene group and surface of MWCNTs. Activated by MMAO, both the iron complexes and immobilized catalysts show high activities for ethylene polymerization. It was possible to evidence that MWCNTs have a great influence on the catalytic activity and on the structure of the resulting polyethylenes. Imino-pyridine nickel complexes containing various kinds of aromatic groups have been synthesized in Chapter IV and polymerization conditions in the presence and in the absence of nanocarbon materials, such as MWCNTs or few layer graphene (FLG), are discussed. For those nickel catalysts bearing 1-aryliminoethylpyridine ligands, the presence of MWCNTs in the catalytic mixture allows the formation of waxes of lower molecular weight and polydispersity, whereas the presence of FLG proved to be beneficial for the catalytic activity. In Chapter V, isoprene polymerization catalyzed by iron complexes containing polyaromatic groups and non-covalently supported on nanoparticles and confined into the inner cavity of MWCNTs (Cat@NPs and Cat@NPs@MWCNTs) are investigated. Iron complexes show excellent activity for the isoprene polymerization and produced high glass temperature polyisoprene with a high trans-1,4-polyisoprene selectivity. Polymer nanocomposites are produced by supported catalysts and, transmission electron microscopy (TEM) evidenced efficient coating of the resulting polyisoprene around the oxygen sensitive iron nanoparticles." Document : Thèse de Doctorat Etablissement_delivrance : Institut National Polytechnique de Toulouse - INPT Date_soutenance : 24/01/2014 Ecole_doctorale : Sciences de la Matière (université Toulouse III P. Sabatier) Domaine : Chimie/Génie chimique En ligne : http://oatao.univ-toulouse.fr/11748/

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