Synthesis and characterization of polymeric ionic liquid through free radical polymerization of acryloyl imidazolium-based ionic liquid monomer

This thesis investigates the synthesis of polymeric ionic liquid [(poly-acryloyloxy)6C6C1im][NTf2], by free radical polymerization of acryloyl imidazolium-base ionic liquid monomer [(acryloyloxy)6C6C1im][NTf2]. Moreover, the smartest synthetic route to obtain this monomer was investigated. Two different synthesis were compared. The first one started from the preparation of the monomer 6-chlorohexyl acrylate followed by substitution and metathesis to reach ionic liquid monomer. The second one started from synthesis of the ionic liquid [(HO)6C6C1im]Cl followed by metathesis and esterification in order to get ionic liquid monomer [(acryloyloxy)6C6C1im][NTf2].

Oxodiperoxomolybdenum catalyzed olefin epoxidation: the role of Ionic Liquids

Ionic Liquids (ILs) constituted by organic cations and inorganic anions are particular salts with a melting point below 100°C. Their physical properties such as melting point and solubility can be tuned by altering the combination of their anions and cations. In the last years the interest in ILs has been centered mostly on their possible use as “green” alternatives to the traditional volatile organic solvents (VOCs) thanks to their low vapour pressure and the efficient ability in catalyst immobilization. In this regard, the subject of the present thesis is the study of the oxodiperoxomolybdenum catalyzed epoxidation of olefins in ILs media with hydrogen peroxide as the oxidant. In particular N-functionalized imidazolium salts, such as 1-(2-t-Butoxycarbonylamino-ethyl)-3-methylimidazolium (1), were synthesized with different counterions [I]-, [PF6]-, [NO3]-, [NTf2]- and [ClO4]– and tested as reaction solvents. The counterion exchange with [Cl]-, [NTf2]- and [NO3]- was also performed in unfuctionalized imidazolium salts such as 3-butyl-1-methylimidazol-3-ium (3). All the prepared ILs were tested in catalytic epoxidation of olefins exploiting oxodiperoxomolybdenum complexes [MoO(O2)2(C4H6N2)2] (4) and [MoO(O2)2(C5H8N2)2] (5) as catalysts. The IL 3[NTf2] and the catalysts 5 give rise to the best results leading to the selective formation of the epoxide of cis-cyclooctene avoiding hydrolysis side reaction. A preliminary study on the synthesis of novel NHC oxodiperoxomolybdenum complexes starting from imidazolium salts was also developed.