Molecular dynamics (MD) simulation studies were considered in this study in the fields of phosphonium based ionic liquids (PBILs) and heterogeneous (solid/liquid) zeolite systems. A new generation of ionic liquids (ILs) called phase-separable ionic liquids (PSILs) are able to dissolve cellulose and lignin, a necessary step, for conversion of biomass to fuels and chemicals with co-solvents and are immiscible with water or saline solutions. Molecular simulations on these systems will provide insights of phase behavior and dissolution phenomenon. The knowledge of interfacial phase behavior of ionic liquids/solvent systems is critical for materials discovery for designing efficient dissolution processes. Transition zone from miscible to immiscible behavior was observed for alkyl chain lengths varying from 6 to 8. Emulsion phase was observed for [P8888]+ ion. Result from molecular dynamics (MD) simulations shows excellent agreement with experimental data for both chloride and acetate anions. These contributions will be helpful in modeling PBILs system for cellulose dissolution, liquid-liquid extraction and biomass studies. Another important aspect in biofuel conversion is glucose isomerization step using zeolites. Zeolites are crystalline solids that have wide applications in industrial areas for its hydrocarbon conversion, adsorption of molecules. In this study, we report MD simulation studies on glucose solution diffusion into zeolite structure as a function of temperature and pressure. Development of united-atom force field for PBILs, for phosphonium cation with anions of chloride and acetate, is considered in this study. Force field parameterization was considered for these ionic liquids with a variation of alkyl chain length in phosphonium ion with chloride and acetate anions. Performance of force field parameters was analyzed by calculating properties such as density and viscosity at various temperature and compared with available experimental data. Efficient algorithm techniques were developed in molecular simulations that will reduce computational load in calculating non-bonded interactions. We introduce theory of local sample (TLS) in calculating non-bonded interactions acting on atoms. Another algorithmic improvement in MD simulations is calculating force acting on atoms based on previous time steps, that achieves up to 50 % reduction in computational time

Phosphonium ions readily compare to ammonium ions in regards to their aggregate characteristics, thermal stability, and antibacterial activity. Ionic aggregation in phosphonium-based polymers provides thermoreversible crosslinks, ideal for reversible self-assembly, self-healing, and smart response. In polymers, these ionic functionalities aggregate, providing improved moduli, and altering the size and structure of ionic aggregates regulates polymer melt processability. This dissertation highlights phosphonium-based chemistry for the synthesis of novel step-growth ionomers and structure-property relationships in ionic polymers. The synthesis of phosphonium endcapping reagents for melt polyester reactions afforded a thermally stable ionic functionality that controlled molecular weight. Weak association was present with phosphonium ions at low ion concentrations below 7.7 mole %. The use of novel ionic bisacetoacetate monomers in the formation of networks from Michael addition reactions led to the synthesis of ionic networks with increased and broadened glass transitions and improved tensile stresses at break and strains at break compared to those in the non-ionic networks. The first electrospun fibers from Michael addition crosslinking reactions are reported, and equilibrium ionic liquid uptake experimental results indicated that ionic functional networks absorb close to three times the amount of ionic liquid as non-ionic, poly(ethylene glycol)-based films. Chain-extending polyurethanes with a phosphonium diol and subsequently varying the hard segment content led to changes in ionic aggregation, crystallinity, and thermal transitions in the polymers. Additionally, novel phosphonium-based methacrylate monomers incorporated into diblock copolymers with styrene exhibited microphase separation. Overall, the inclusion of phosphonium ions pendant to or in the main chain of various types of polymers led to changes in morphology, improved tensile properties, enhanced moduli, broadened transitions, changes in crystalline melting points, changes in solubility, and appearance of ionic aggregation. / Ph. D.

La première partie des travaux présentés dans ce mémoire concerne la synthèse d'hétérocycles à motifs azo (N2) fondée sur une étape clef pallado-catalysée. Il a ainsi été démontré que deux familles d'hétérocycles diazotés étaient sélectivement accessibles à partir de précurseurs communs : des hydrazones C-homo-allyliques. Des cycles mono-insaturés à cinq chaînons de type pyrazoline ou à six chaînons de type tétrahydropyridazine ont été ainsi préparés par réaction de N-vinylation ou N-allylation CH-oxydante intramoléculaire catalysée par des complexes de palladium(II) à ligands phosphines. Il a été montré que l'issue du processus est fonction de la basicité des ligands ioniques (de type X) du sel de palladium(II) précurseur de l'espèce catalytique. L'utilisation de Pd(OAc)2 favorise ainsi la formation de 6-methylidène-1,4,5,6-tétrahydropyridazines via un processus 6-endo/exo trig, alors qu'un complexe plus électrophile [Pd(MeCN)2]X2; X = OTs, OTf conduit aux 5-vinylpyrazolines suivant un processus 5-exo trig. L'efficacité particulière des ligands faiblement donneurs tels que l'imidazolophosphine " BIPHIMIP " a été ici mis en évidence. Les 5-vinylpyrazolines et les 1,4,5,6-tétrahydropyridazines obtenues ont ensuite été sélectivement transformées en leurs dérivés aromatiques respectifs, à savoir des 5-vinylpyrazoles et 6-méthylpyridazines, selon un processus d'isomérisation-élimination séquentiel. L'application de cette méthode de synthèse à des substrats di- et tri-hydrazones C-homo-allyliques a permis d'accéder à des systèmes tri- ou tétra-aromatiques, en particulier à des pyridazylbenzènes analogues des terphényles ou triphénylbenzènes dont les propriétés électroniques d'absorption et de fluorescence ont été systématiquement étudiées. La deuxième partie de ce mémoire est consacrée à l'étude de nouveaux ligands phosphorés à caractère donneur " extrême " tels que des ligands imidazolo- et cyclopropénio-phosphines à caractère donneur particulièrement faible. En série neutre, des ligands mono-, di- et tri-imidazolophosphines ont ainsi été caractérisés et utilisés en catalyse de fonctionnalisation de liaisons CH allyliques pour la préparation d'azo-hétérocycles décrite dans la 1ère partie. En série cationique, des cyclopropéniophosphines de deux types ont été préparées : des bis-diisopropylamino-cyclopropénio(hydroxy)phosphines et des bis-diisopropylamino(dicyclopropénio)phosphines, obtenues par réactions d'une dichloro-phosphine avec un carbène libre de type cyclopropénylidène. La réactivité et la chimie de coordination avec des métaux de transition (Pd, Rh, Au, Cu, Pt) de ces ligands cationiques a été ensuite étudiée. En série bis-diisopropylamino(dicyclopropénio)-P-ter-butyle, un complexe tétranucléaire de palladium dicationique comportant deux ligands phosphido a été isolé. L'élimination du P-substituant ter-butyle a été attribuée à une forte contrainte électrostatique présente au sein du complexe. Enfin, lors de la tentative d'accès à de nouveaux ylures de phosphonium C-substitués par un motif cyclopropényle, un réarrangement original a été observé. Des vinylphosphoniums C-substitués par un hétérocycle à quatre chaînons de type azétidine ont été ainsi obtenus et entièrement caractérisés. / The first part of the work thesis concerns the synthesis of heterocycles with an azo (N2) pattern based on a pallado-catalyzed key step. It has been shown that two families of dinitrogen heterocycles were selectively accessible from the same precursors, namely C-homo-allylic hydrazones. Mono-unsaturated five-membered rings pyrazolines or six-membered tetrahydropyridazines were thus prepared by N-vinylation or N-allylation through CH-oxidative intramolecular reaction catalyzed by palladium(II) complexes with phosphine ligands. It was shown that the outcome of the process depends on the basicity of the ionic ligands (of type X) of the palladium(II) salt precursor of the catalytic species. The use of Pd(OAc)2 was thus found to promote the formation of 6-methylidene-1,4,5,6-tetrahydropyridazines via a 6-endo/exo-trig process, while a more electrophilic complex [Pd(MeCN)2X2]; X = OTs, OTf, lead to 5-vinylpyrazolines via a 5-exo trig process. The particular efficiency of weakly donating ligands such as the imidazolophosphine "BIPHIMIP" has been highlighted here. The obtained 5-vinylpyrazolines and 1,4,5,6-tetrahydropyridazines were then selectively derivatized to their respective aromatic analogues, namely 5-vinylpyrazoles and 6-methylpyridazines, through a sequential isomerization-elimination process. Application of this synthesis method to di- and tri- C-homo-allylic hydrazone substrated allowed access to tri- or tetra-aromatic systems, in particular to poly-pyridazine analogues of terphenyls or triphenylbenzenes whose absorption and fluorescence properties have been systematically studied. The second part of the thesis is focused on the study of novel phosphorus ligands with "extreme" donor character. In particular, imidazolo- and cyclopropenio-phosphine ligands with a particularly weak donor character have been synthetized. In the neutral series, mono-, di- and tri-imidazolophosphines have been characterized and used in catalysis of allylic C-H bond functionalisation for the preparation of azo-heterocycles described in the first part. In the cationic series, two types of cyclopropeniophosphines were prepared: the bis-diisopropylamino-cyclopropenio(hydroxymethyl) phosphines and the bis-diisopropylamino-(dicyclopropenio)phosphines, obtained by reaction of a dichlorophosphine with a free carbene of the cyclopropenylidene type. The reactivity and coordination chemistry of the latter cationic ligands with transition metals (Pd, Rh, Au, Cu) were then studied. In the bis-diisopropylamino(dicyclopropenio)-P-tert-butyl series, a dicationic tetranuclear complex of palladium with two phosphido ligands was isolated. The elimination of the P-tert-butyl substituent was attributed to a strong electrostatic constraint within the complex. Finally, when trying to access novel electron-rich phosphonium ylides C-substituted by a cyclopropenyl moiety, an original rearrangement was observed. Vinylphosphoniums C-substituted by a four-membered heterocycle of the azetidine type have thus been obtained and fully characterized.

Les liquides ioniques sont des produits chimiques avancés promis selon de nombreuses personnes à un brillant avenir dans un certain nombre d’applications stratégiques qui pourraient servir un avenir plus vert dans la chimie et les développements technologiques liés à l'énergie. Cependant, le manque de données thermodynamiques appropriées ainsi que les discours réducteurs portant sur une haute stabilité thermique et l’absence de tout danger intrinsèque comme tendances absolues de ces produits chimiques ont conduit à entreprendre ce travail de thèse avec comme objectif de développer une méthodologie dédiée et pertinente visant à caractériser les profils de dangers physico-chimiques de ces molécules chimiques. En effet, étant donné le nombre potentiellement élevé de liquides ioniques, une meilleure stratégie consistant à explorer les propriétés réelles de ces matériaux, sans négliger les risques physico-chimiques potentiels, y compris les risques d’incendie, constitue une contribution de taille à leur utilisation verte. A cet effet, des outils expérimentaux ont été mis en œuvre et utilisés, les résultats obtenus confirment jusqu’ici que le potentiel de dangers physico-chimiques doit être évalué au cas par cas.Finalement, les perspectives concernant les travaux futurs en ce qui concerne une meilleure connaissance et une appréciation des questionnements liés aux dangers physico-chimiques sont donnés dans le but de servir une conception et une utilisation durable des liquides ioniques. / Ionic liquids are advanced chemicals promised according to many people to a brilliant future in a number of strategic applications that might serve greener future in chemistry and energy related technological developments. However, lack of appropriate thermodynamic data as well as some what misleading discourse advocating on high thermal stability and absence ofany intrinsic hazard as absolute trends of these chemicals have led to initiate this thesis workwith the objective to develop a dedicated and pertinent methodology aiming at characterizing the comprehensive physico-chemical hazards profile of such chemical.Indeed, given the huge potential number of ionic liquids, a better strategy consists in exploring real world properties of these materials, not neglecting potential physico-chemical hazards,including the fire hazards, as to contribute to their green use. For that purpose, experimental tools have been implemented and used; obtained results so far confirm that the physico-chemical hazards potential must be assessed on a case by case approach. Finally, perspectives regarding future work with regard to better knowledge and assessmentof ionic liquids physico-chemical related issues are given with the aim of serving sustainable design and use of ionic liquids.

A extratibilidade de sais de fosfônio foi aproveitada para elaborar método de separação Ir-Rh, mediante a extração do sal de trifenil n-propil fosfônio do cloro-complexo de Ir(IV,) em clorofórmio. O coeficiente de extração de 99,2%, permite retirar o irídio do meio aquoso com grande eficiência. O irídio assim separado é determinado diretamente, por via espectrofotométrica, em 494 mµ, em faixa de concentração de 5,0 a 50,0 µg/ml. Pd(II), Pt(IV) e Os(IV) interferem e são eliminados previamente, assim como Au(III). Os ânions interferentes, I-, Br- e SCN- são também eliminados previamente. Muitos íons podem estar presentes, tais como Co(II),Cu(II), Mn(II), Fe(III), Ni(II), As(V), Sb(V), NO3-, ClO4- e SO4--. Após a separação do Ir (IV), o Rh(III) que permanece, na solução é complexado com íons azoteto e extraído em clorofórmio depois de precipitado com íons trifenil n-propil fosfônio, sendo o coeficiente de extração de 98,3%. A determinação ê também feita no próprio solvente, mediante medida espectrofotométrica em 404-408 mµ, para um intervalo de concentração de . 10,0 a 70,0 µg/ml. Uma separação envolvendo Os(IV), Pd(II)e Pt(IV) foi elaborada, eliminando-se Pd(II) e Pt(IV) por extração de ambos em metil n-butil cetona a partir de uma solução contendo SCN-. O Os(IV) é determinado na solução aquosa na forma de OsC16-- por medida espectrofotométrica em 370 mµ, válida para a faixa de concentração de 2,0 a 20,0 µg/m1. / Abstract not available.

This thesis aims at developing a method of chemical aftertreatment for reduction of free formaldehyde release of a tetrakis (hydroxymethyl) phosphonium chloride (THPC) urea precondensate, ammonia cured durable flame retardant finished cotton fabric, by preventing the formation of free formaldehyde. Formaldehyde is toxic and carcinogenic. According to the worldwide standards, acceptable limit of free formaldehyde release, for the fabrics that have skin contact, is only 75 ppm (measured by water extraction method). In this research, a cotton fabric flame retardant finished in an industrial plant in Pakistan is used. Fabric is finished by the application of THPC urea precondensate and ammonia cured, oxidized and washed. After finishing, it is not aftertreated with sodium metabisulfite that is a commonly used aftertreatment method for the reduction of free formaldehyde release. Aftertreatment with sodium metabisulfite has various problems that include large number of hot washings and there is an increase in the formaldehyde release during fabric storage. If the fabric has 75 ppm of free formaldehyde, there is often an increase in free formaldehyde release during fabric storage. There is a very limited research on the aftertreatment methods and few reports of application of these aftertreatments on flame retardant fabrics have been published. In this research, two methods of aftertreatments are developed to reduce the free formaldehyde contents to 75 ppm or less. One is the aftertreatment with a combination of resorcinol 1% and diethylene glycol 4%. The other is the combination of resorcinol 1% and boric acid 6%. For both these aftertreatments, ammonium acetate 0.5% is used as a catalyst. Fabric is padded with the solution and then dried at 130̊ C for 8 minutes. After drying, fabric is rinsed with water at 40̊ C. The aftertreatment methods developed in this research have shown a long term effect in keeping the formaldehyde release below 75 ppm during fabric storage that is not available with other conventional aftertreatment methods. These aftertreatment methods have no adverse effect on the flame retardancy of the THPC ammonia cured finished fabric and the fabric is soft as compared to the original flame retardant finished fabric and to the fabric after treated with existing methods. These new developed methods have industrial application because there is no use of any solvent and there is no use of any special equipment for the aftertreatment.

No description available.

The potential use of Resadiye/Tokat bentonite as a reinforcement in polypropylene (PP) and linear low density polyethylene (LLDPE) polymer matrix nanocomposites filler was investigated. At first, organoclays (OC) were prepared by cation exchange reaction (CER) between the raw bentonite (RB) and three quaternary ammonium salts with long alkyl tails (QA): hexadecyl trimethyl ammonium bromide [HMA] [Br], tetrabutyl ammonium tetrafluoroborate [TBA] [BF4], tetrakisdecyl ammonium bromide [TKA] [Br] and one quaternary phosphonium (QP) salt: tetrabutyl phosphonium tetrafluroborate [TBP] [BF4]. Characterization of resulting materials by XRD, TGA, FTIR and chemical analysis confirmed the formation of organoclays. Ternary composites of PP/organoclay/ maleic anhydride grafted polypropylene (MAPP) were prepared with two different grades of PPs in a co-rotating twin screw extruder. Composites prepared with these organoclays and PPs showed microcomposite formation. In the second part of the study, raw bentonite was purified by sedimentation, and characterization of purified bentonite (PB) by XRD, cation exchange capacity (CEC) measurement and chemical analysis (ICP) confirmed the success of purification method. PB was then modified with two QA`s: dimethyl dioctadecylammonium chloride [DMDA] [Cl], tetrakis decylammonium bromide [STKA] [Br] and one QP: tributyl hexadecyl phosphonium bromide [TBHP] [Br]. Organoclays from PB were used with the PP with lower viscosity, and ternary nanocomposites (PP/Organoclay2/MAPP5) were prepared in the extruder followed by batch mixing in an intensive batch mixer. Use of DMDA and TBHP OCs resulted in nanocomposite formation, while STKA resulted in microcomposite formation as observed by XRD and TEM. Young`s modulus and yield stress of the samples were enhanced through nanocomposite formation. In the last part of the study, ternary composites of LLDPE/Organoclay/ compatibilizer, a random terpolymer of ethylene, butyl acrylate and maleic anhydride (E-BA-MAH, Lotader&reg / 3210), were prepared by melt compounding in the batch mixer at two different clay concentrations (2 and 5 wt %) and fixed compatibilizer/organoclay ratio (&alpha / =2.5). A commercial organoclay, I34, was also used in LLDPE based nanocomposites to make a comparison. XRD and TEM analyses of the compounds prepared by DMDA and TBHP showed mixed nanocomposite morphologies consisting of partially intercalated and exfoliated layers. Young`s modulus and tensile strength of nanocomposites prepared with DMDA and TBHP showed generally higher values compared to those of neat LLDPE, while results were the highest in the composites prepared with commercial organoclay I34. Parallel disk rheometry was used as a supplementary technique to XRD, TEM and mechanical characterizations, and it was shown to be a sensitive tool in assessing the degree of dispersion of clay layers in the polymer matrix.

A extratibilidade de sais de fosfônio foi aproveitada para elaborar método de separação Ir-Rh, mediante a extração do sal de trifenil n-propil fosfônio do cloro-complexo de Ir(IV,) em clorofórmio. O coeficiente de extração de 99,2%, permite retirar o irídio do meio aquoso com grande eficiência. O irídio assim separado é determinado diretamente, por via espectrofotométrica, em 494 mµ, em faixa de concentração de 5,0 a 50,0 µg/ml. Pd(II), Pt(IV) e Os(IV) interferem e são eliminados previamente, assim como Au(III). Os ânions interferentes, I-, Br- e SCN- são também eliminados previamente. Muitos íons podem estar presentes, tais como Co(II),Cu(II), Mn(II), Fe(III), Ni(II), As(V), Sb(V), NO3-, ClO4- e SO4--. Após a separação do Ir (IV), o Rh(III) que permanece, na solução é complexado com íons azoteto e extraído em clorofórmio depois de precipitado com íons trifenil n-propil fosfônio, sendo o coeficiente de extração de 98,3%. A determinação ê também feita no próprio solvente, mediante medida espectrofotométrica em 404-408 mµ, para um intervalo de concentração de . 10,0 a 70,0 µg/ml. Uma separação envolvendo Os(IV), Pd(II)e Pt(IV) foi elaborada, eliminando-se Pd(II) e Pt(IV) por extração de ambos em metil n-butil cetona a partir de uma solução contendo SCN-. O Os(IV) é determinado na solução aquosa na forma de OsC16-- por medida espectrofotométrica em 370 mµ, válida para a faixa de concentração de 2,0 a 20,0 µg/m1. / Abstract not available.

The objective of this research is to explore the use of ionic liquds in crystal engineering and drug delivery. Ionic liquids have a wide range of applications in pharmaceutical field due to their unique physicochemical propertie ssuch as chemical, thermal stability, low melting point, nonvolatility, nonflamability, low toxicity and recyclability which offer unique and interesting potential for pharmaceuitcal applications. Currently, many research groups are working on the development of ionic liquids to use in this field but there is need to develop systematic understanding about new techniques for synthesis and applications of ionic liquids to obtain new crystal form and potential of drug ionic salts. The synthesis of fifteen phosphonium ionic liquids under microwave irradiation and their physicochemical properties was investigated. The reaction time was significantly reduced compared to conventional methods, and higher yields were reported. The crystallisation of pharmaceutical drugs such as sulfathiazole, chlorpropamide, phenobarbital and nifedipine were investigated using imidazolium ionic liquids. The supramolecular complex of sulfathiazole and phenobarbital with imidazolium ionic liquids and polymorphic change in chlorpropamide was achieved. The ionic liquids provides unique environment for the crystallisation. The imidazolium salts of ibuprofen and diclofenac were synthesised and evaluated for physicochemical properties and their pharmaceutical performances especially transdermal absorption. The investigation of physicochemcal properties and pharmaceutical performance of imidazolium drug salts indicated opportunity to optimise lipophilicity and other physicochemical properties such as molecular size, osmolality, viscosity to achieve desired skin deposition and permeation. This study will provide a new approach to design of new drug salts develop using the interdisciplinary knowledge of chemical synthesis and drug delivery. / Social Justice Department, Government of Maharashtra, India.