Single (SWNTs) and multiwalled (MWNTs) carbon nanotubes were functionalized with a titanium alkoxide catalyst through a Diels-Alder cycloaddition reaction. The catalyst-functionalized carbon nanotubes (CNTs) were used for the surface initiated titanium-mediated coordination polymerizations of L-lactide (L-LA),-caprolactone ( -CL) and n-hexyl isocyanate (HIC) employing the "grafting from" technique. 1 H NMR, IR and Raman spectra showed that the precursor catalyst was successfully synthesized and covalently attached on the CNTs surface. Thermogravimetric analysis (TGA) revealed that the grafted poly(L-lactide) (PLLA) content could be controlled with time. The final polymer-grafted CNTs were readily dissolved in organic solvents as compared to the insoluble pristine and catalyst-functionalized CNTs. The presence of thick layers of polymers around the CNTs was observed through transmission electron microscopy (TEM). Differential scanning calorimetry (DSC) proved that the glass transition (T g ) and melting (T m ) temperatures of the PLLA are affected by the presence of the CNTs, while PLLA R-helix conformation remains intact, as revealed by the circular dichroism (CD) spectra.
A novel nickel-based complex coordinated with an asymmetric diphosphinoamine ligand was synthesized and fully characterized. Single crystals of good quality were also obtained, and the solid-state structure of the complex was studied via X-rays diffraction. The catalytic activity of this Ni(II) complex in the vinyl-type polymerization of norbornene was studied with methylaluminoxane (MAO) as the cocatalyst/activator. The influence of the reaction time, the equivalents of MAO used, and the concentration of the monomer on: (i) the activity of the catalytic system; (ii) the isolated yield of the polymer; and (iii) the molecular weight and molecular weight distribution of the polymer were investigated. The isolated polynorbornene (PNB) yields are significantly higher compared with those reported for other similar nickelbased systems. The as-obtained PNBs are characterized by high molecular weights and relatively narrow and monomodal molecular weight distributions (amongst the narrowest reported in the literature). The linear dependence of the molecular weight of the obtained PNB on the concentration of norbornene points toward a controlled polymerization reaction.
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