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Synthesis Novel Ni(Ⅱ) And Pd(Ⅱ) Complexes Bearingβ-Benzocyclohexan-ketoarylimine Ligands And Their Catalytic Copolymerization Of Norbornene

Posted on:2013-07-08Degree:MasterType:Thesis
Country:ChinaCandidate:Y M LiuFull Text:PDF
GTID:2231330374464460Subject:Polymer Chemistry and Physics
Abstract/Summary:PDF Full Text Request
The condensation of aromatic amines with (3-diketone was carried out to afford the corresponding p-benzocyclohexan-ketoarylimine ligands, the ligands and or Et4N]2PdCU evidenced ligand exchange eifect, the novel Ni(Ⅱ) and Pd(Ⅱ) complexes bearing P-benzocyclohexan-ketoarylimine ligands colored invisible green, brownish yellow are produced successfully. The general structure of complexes is following: Mt(p-ben2ocyclohexan-ketoarylimino)2{Mt(bchkai)2: bchkai=C10H8(O)C[N(aryl)CH3]; aryl=naphthyl, fluoryl; Mt=Ni, Pd}. The structure was determined by X-ray diffraction, the N, O atoms, the central metal atom and benzocyclohexyl form a stable coplanar six-membered ring, the aromatic ring connected to N atoms is vertical118.91°to the plane, Meanwhile the novel Ni(Ⅱ) and Pd(Ⅱ) complexes using Copolymerization of Norbornene is explored.A serial of late transition metals complexes, which bearing p-benzocyclohexan-ketonaphthylimine ligand Mt(β-benzocyclohexan-ketonaphthylirnino)2{Mt(bchkni)2: bchkni=C10Hg(O)C[N(naphthyl)CH3]; Mt=Ni, Pd} and bearing P-benzocyclohexan-ketofluorylimine ligand Mt(p-benzocyclohexan-ketofluorylimino)2{Mt(bchkfi)2: bchkfi=C10H8(0) C[N(fluoryl) CH3]; Mt=Ni, Pd} activated by B(C6F5)3, the catalytic systems exhibited high activities toward the homo-polymerization of norbornene (NB)(as high as2.7×105gpoiymer/molNih for Ni(bchkai)2and2.3×105gPolymer/molpd·h for Pd(bchkai)2, respectively). The obtained polynorbornene (PNB) was completely soluble in chlorobenzene and dichlorobenzene at room temperature and partly dissolved in chloroform, the molecular weights of the PNB obtained by Ni(bchkni)2catalytic system isl.9><105, the narrow molecular weight distribution is smaller than2. The PNB obtained by another systems can not detect because of the concentration of the soluble portion of PNBs was fully enough for GPC analysis. All the PNBs exhibited good thermal stability (Td>420℃)Two novel late transition metals complexes Ni(bchkni)2and Pd(bchkni)2catalytic systems showed high activity toward the copolymerization of NB with1-octene under various polymerization conditions and the produced copolymers showed good solubility in common organic solvents. From the GPC, NMR, FTTR we khow the copolymer with relatively high molecular weights (0.1-1.4×105g/mol) as well as narrow molecular weight distribution (PDI<2) is addition-type copolymer. The1-octene content in the copolymers can be controlled up to8.9-14.0%for Ni(bchkni)2and8.8-14.6%for Pd(bchkni)2catalytic system by varying comonomer feed ratios from10to70mol%. The reactivity ratios of two monomers were determined to be r1-octene=0.052, rNB=8.45for Ni(bchkni)2system, and r1-octene=0.025, rNB=7.17for Pd(bchkni)2system by the Kelen-TUdOs method. From the XRD, TGA, DSC the achieved NB/1-octene copolymers were confirmed to be noncrystalline and exhibited good thermal stability (Td>400℃, Tg=244.1-272.2℃).A serial of late transition metals complexes Ni(bchkni)2, Pd(bchkni)2, Ni(bchkfi)2, Pd(bchkfi)2catalytic systems were effective for copolymerization of NB and5-norbornene-2-carboxylic acid methyl ester (NB-COOCH3) in relatively high activities (0.1-2.4×105gpolymer/molMt·h) and produced copolymers with relatively high molecular weights (0.5×105-1.2×105g/mol) as well as narrow molecular weight distributions (PDI<2for all polymers). According to the NMR and FTIR we can found that the copolymerization of NB and the NB-COOCH3occurred via a vinyl polymerization mode. Influences of the metals and co-monomer feed content on the polymerization activity as well as on the incorporation rates (20.9-42.6%) were investigated. The achieved NB/NB-COOCH3copolymers were confirmed to be noncrystalline (measured by XRD) and exhibited good thermal stability (Td>400℃). The copolymers obtained by Ni(bchkai)2in the chlorobenzen can form films, from the UV-vis the films exhibited good mechanical properties and they also show high transparency.
Keywords/Search Tags:nickel catalyst, palladium catalyst, late transition metals complexes, norbornene, vinyl-addition copolymerization
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