الفهرس 
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Abstract
Recently, ionic liquids (ILs) and polyionic liquids (PILs) as green chemicals attracted great attention to be applied in different applications such as petroleum industry, water treatment and nanomaterial preparations. The best selection of the most popular types of ILs cations such as imidazolium, pyridinium, alkylammonium, alkylphosphonium, pyrrolidinium, and guanidinium affected the unique properties of ILs. Hydrophobic and amphiphilic ILs and PILs can replace surfactants used to solve many petroleum problems such as enhanced oil recovery, demulsifiers, corrosion inhibitors, asphaltene and oil spill dispersants and refining extraction solvents. The formation of water in oil (W/O) or oil in water (O/W) emulsions increases the viscosity of crude oil, affects the crude oil transportation and raises the production cost. ILs containing both either amphiphilic cations or anions have strong ability to reduce the IFT between the crude oil and sea water and replace the asphaltene from the surface of water in oil (W/O) or oil in water (O/W) emulsions.
Furthermore, the capping of nanomaterials with environmentally friendly ionic liquids (ILs) and polyionic liquids (PILs) can control their sizes and modify their surface properties to be used for different industrial applications such as oil spill collection and water treatment.
Also, crosslinking of polyionic liquids can be used to prepare porous materials that can successfully remove pollutants from drinking water. Crosslinking of PILs can occur using difunctionalized monomers. Furthermore, nanomaterials can be introduced to the crosslinked PILs in order to enhance their performance.
In this study, hydrophobic and amphiphilic ILs and PILs were prepared and applied in petroleum industry. Hydrophilic PILs were synthesized and used in nanomaterial preparations and applied for water treatment. Crosslinked PILs were also prepared and applied in water treatment.
The original work of this thesis includes the preparation of new hydrophobic, amphiphilic and hydrophilic ILs and PILs and their applications in water treatment, nanomaterial preparations and petroleum applications. Also, the synthesis of new crosslinked PILs and their applications in dye removal and water purification is reported.
• Hydrophobic ionic liquids containing imidazolium cations, 1-allyl-3-methylimidazolium cardanoxy (AMIMCO), 1-allyl-3-methylimidazolium oleate (AMIMO) and 1-allyl-3-methylimidazolium abietate (AMIMA) were successfully prepared via ion exchange as shown in Scheme 1 to reduce asphaltenes precipitation during petroleum recovery and transportation of heavy crude oil. The data showed that the ILs have alicyclic hydrophenanthrene ring (AMIMA) interacted as ionic liquids with asphaltenes confirmed more than that having alkyl (AMIMO) or alkyl phenol (AMIMCO) ILs and the interaction took place through charge transfer more than π-π interactions. The data confirmed that the zeta potential (mV) or surface charges of asphaltene became more negative in the order of AMIMCO>AMIMO>AMIMA. This means that the asphaltene became more hydrophilic in the presence of AMIMCO and more hydrophobic in the presence of AMIMA. These data confirm that the dispersion of asphaltene in heptane increased in the order AMIMA>AMIMO>AMIMCO.
Scheme 1: Synthesis of AMIMO, AMIMA and AMIMCO using ion exchange technique.
• Superhydrophobic magnetite was prepared using hyrophobically modified 1-allyl-3-immidazolium oleate ionic liquid (AMIMO) as displayed in Scheme 2. The prepared magnetite nanoparticles showed monodispersity via superparamagnetism characteristics. Moreover, the produced magnetite has mesoporous structure and achieved high oil collection efficiencies at low concentrations.
Scheme 2: Capping of magnetite with AMIMO.
• One-pot synthesis of dialkyl imidazolium ionic liquids were carried out in the presence of acetic acid followed by ethoxylation with tetraethylene glycol to produce amphiphilic ILs as shown in Scheme 3. The surface tension measurements confirmed the surface activities of the prepared ILs. They behave like surfactants due to successive adsorption of both cations and anions at interfaces. The DLS measurements elucidate that, these new ILs had the ability to form aggregates above the cac in both aqueous and toluene solvent with Dh ranged from 0.1−55 nm. The etherified ILs were used as demulsifiers for heavy crude oil/ sea water emulsions. The demulsification data confirm that the presence of two dodecyl hydrophobic group, oxyethylene units in the chemical structure of EDDI facilitate their dispersion in the crude oil to surround the water droplet in crude oil emulsions more than EDHI.
Scheme 3: Preparation and ethoxylation of imidazolium based ILs.
• Cardanol as Cashew nut shell oil with m-pentadecyl phenol chemical structure was modified by incorporation of the hydrophilic amines and glycol to obtain new amphiphilic PILs (Scheme 4 and 5). The surface tension measurements showed that, the QDECA has greater tendency to reduce the surface tension of water than QTECA. The higher reduction of the water surface tension for QDECA than QTECA confirms the weak intermolecular interaction between ions (low zeta potential values), as well as, the hydrophobicity of cardanol cations. The IFT, surface tension and asphaltene dispersion data elucidate the strong ability of PILs to reduce the crude oil/ water interfacial tension. QTECA and QDECA were applied as asphaltene dispersants and demulsifiers for heavy crude oil/ sea water emulsions. QTECA showed higher asphaltene dispersant efficiency than QDECA and that can be referred to the adsorption of cardanol positive charges cations on the asphaltene negative charges. The demulsification data confirmed that the QTECA and QDECA achieved high separation performances and demulsifying action reached 100 % at low concentration 10 mg.L-1 during 30 minutes for crude oil / water (90/10 Vol %) emulsion.
Scheme 4: Synthetic route of QTECA as new PIL.
Scheme 5: Synthetic route of QDECA as new PIL.
• New protic PIL was prepared by the quaternization of AMPS monomer with DEEA followed by copolymerization with VP monomer to produce PAMPSA/VP (Scheme 6). The prepared PIL was used as capping agent during the synthesis of ZnO nanoparticles at room temperature (Scheme 7). The presence of VP in PIL chemical structure increases the reactivity of PAMPSA/VP to control the shape and size of ZnO nanoparticles. The interaction between amide groups of VP may inhibit the growth of ZnO nanoparticles through coordination bond created between nitrogen atom of the VP and the Zn 2+ ion. Zeta potential measurements of ZnO colloidal solution illustrate that the negative charges of PIL surrounded to ZnO produced from the direction of sulfonate groups of PIL to exterior surfaces of ZnO nanoparticles. The prepared ZnO nanoparticles were dispersed with different percentages during the formation of AMPS/AN hydrogel to synthesize ZnO-AMPS/AN nanocomposite which showed high removal efficiencies and rates for MB dye from water than that used without ZnO nanoparticles.
Scheme 6: Preparation of PIL based on PAMPSA-VP.
Scheme 7: Synthesis of Zn(OH)2 and ZnO nanoparticles.
• The PIL based on PAMPSA/VP was also used as capping agent to synthesize Fe3O4 and Ag NPs as new catalysts Scheme 8 and 9, respectively. The PAMPSA/VP-Ag and PAMPSA/VP-Fe3O4 NPs showed good thermal and chemical stability against oxidation. The thermal stability data elucidate that the contents of magnetite and silver were 19.2 and 39.4 Wt. %, respectively. Zeta potential measurements indicated that the negative surface charges of PAMPSA/VP-Ag and PAMPS/VP-Fe3O4 in acidic and neutral pHs confirms the formation of protic PAMPSA/VP as shell which increases the dispersion of both PAMPSA/VP-Fe3O4 and PAMPSA/VP-Ag NPs in water. The formation of superparamagnetic Fe3O4 NPs facilitate their application as Fenton oxidation catalyst to complete degradation of MB dye without formation of intermediate during short time of 8 minutes. Moreover, the formation of highly dispersed Ag NPs activate their application as catalyst to the discoloration of MB by converting its oxidized form to reduced one in short reaction time.
Scheme 8: Synthesis of PAMPSA/VP-Fe3O4 NPs.
Scheme 9: Synthesis of PAMPSA/VP-Ag NPs.
• New PAMPSA-AAT, PAMPSA-AAm, and PAMPSA-HEMA crosslinked PILs cryogels were prepared by quaternization of AMPS and AA monomers with triethanol amine (TEA) followed by crosslinking copolymerization of AMPSA IL monomer with AAT, AAm or HEMA monomers in the presence of MBA to form cryogels at freezing temperature (Scheme 10). The crosslinking polymerization at freezing temperature tunes the distribution of the AMPSA species along the network copolymer chains, form micro and macro pores and modify the thermal stability of the prepared crosslinked PILs. The interconnected pores were formed during the crosslinking copolymerizations of AMPSA-AAT, AMPSA-AAm at freezing temperature while they were not formed in AMPSA-HEMA. The prepared crosslinked PILs were applied as adsorbents for MB dye from aqueous solutions. The main adsorption mechanisms of MB dye onto the surface of the crosslinked PILs cryogels is occurred by the electrostatic interactions of PILs sulfonate and carboxylate anions and the positive charges of MB which enhanced by polymer porosity and the ordering of the internal PILs networks (Scheme 11). Moreover, it was found that the chemical adsorption phenomenon is preferred for PILs adsorbents had the order is PAMPSA-AAT > PAMPSA-AAm > PAMPSA-HEMA.
• The synthesized IL and PILs were characterized using common spectroscopic tools including 1H-NMR, 13C-NMR and FT-IR. The synthesized nanomaterials and nanocomposites were characterized using FTIR, XRD, TEM, SEM, TGA and DLS.
Scheme 10: Formation of PILs networks during cryogelation.
Scheme 11: Ion exchange mechanism of MB with PAMPSA-AAT networks.