Unilever would like to explore the use of functional polysaccharides in then detergency formulations. The aim of this work was to grow various polymer chains of pre-determined lengths via Atom Transfer Radical Polymerisation (ATRP), from a water-soluble polysaccharide and to understand and improve the process. This work has given Unilever the option to fine tune polysaccharide-graft-copolymers for industrial use, whilst also satisfying a full investigation of these novel initiators, using new techniques developed within this work. In this respect, 'controlled or living' growth of chains from a post-modified, water soluble polysaccharide is reported for the first time using the following water soluble monomers: 4-styrene sulfonic acid sodium salt, 2-(dimethylamino)ethyl niethacrylate, poly(ethylene glycol) methacrylate and sodium methacrylate. Examples of psuedo first order control plots were seen, with linear increase in molecular weight (PDi values from 2 to 1.2) and with high monomer conversions. The addition of a non-ii ATRP appeared to increase monomer conversion.

Bleach activators are used in combination with hydrogen peroxide in laundry detergents across the globe to improve the bleaching performance at lower wash temperatures. There are four main activators which are significant on the world market, all of which are solid at room temperature. In household detergents, the incorporation of bleach activators in liquid detergent products has been limited due to incompatibility with other components in solution. In this work, more than 30 novel ionic liquids derived from known and commercially available bleach activators were prepared. The bleach activators, which were available as sodium salts, underwent a facile metathesis reaction with chloride compounds in propanone to form the ionic liquids. Ionic liquids were formed using several different types and sizes of cation, with product physical states varying from liquid or gel to crystalline or waxy so lids. As expected from lattice energy theory, larger and unsymmetrical cations formed products with the lowest melting points, several of which were liquid at room temperature. All novel ionic liquid bleach activators were characterised by several techniques including NMR analysis, microanalysis and ES Mass spectroscopy. As this is the first time bleach activators have been incorporated in ionic liquids, it was unknown what affect this would have on the bleaching ability of the activators. Solution bleaching reactions using the dye Tropaeolin 0 were performed . The dye concentration of the solution was measured by electronic absorption spectroscopy over time. It was found that in most cases the ionic liquid did not have a negative impact on bleaching. One exception was pyridinium cations, the presence of which appeared to prevent the bleaching reaction from occurring at all. Cations which had surface-active properties were found to increase the bleaching rate.

Surfactants, the main ingredient of detergent formulations, have the ability to adsorb at air/water interfaces due to their amphiphilic nature. Surfactants can, therefore, be used as excellent foam stabilising agents in several systems, eliminating or preventing major destabilisation phenomena including drainage, coalescence and disproportionation. In this project the addition of a small concentration of surface active or non- surface active components to the surfactant-stabilised system; has been studied in relation to their ability of improving the foam stability of the system. Several additives have been examined as .to their ability to act as effective foam stabilizers. These included surface active proteins, polymers and surface and non-surface active particles. Probably the most effective foam stabilising material was a particle material formed after the complexation of Ethylcellulose with Cellulose. This complex, along with other additives that showed a modest improvement on the foam stability of the surfactant stabilised system, has been tested on their ability of resisting to bubble coalescence, disproportionation and drainage phenomena. Most of the tests have been completed using equipment specially designed at the workshop of the School of Food Science and Nutrition, University of Leeds. The surface activity of the surfactant system on its own and in the presence of the stabilising additives was measured in relation to the surface tension and the surface viscoelasticity properties of the systems in order to determine the mechanism of action of these stabilising additives. It has been shown that the possible mechanism of action is one that the particles are adsorbing at the interface acting synergistically with the surfactant and effectively enhance the foam stability of the system. Another possible way of stabilising could be that the particles are collected in the plateau borders and this slows down the liquid drainage and therefore the thinning and rupture of the lamellae. Confocal Laser Scanning Microscopy~ (CLSM) was used to exarrune the structure of the EC-C complex and explore how it is adsorbed at the interface in order to stabilise the bubbles on its own and at the presence of the anionic surfactant. As it has been concluded the particles are probably adsorbed at the bubble interface and even though the surfactant predominates at the interface the appearance of a certain concentration of particles can be seen through the confocal images, indicating that the complex is strongly adsorbed at the interface.

Sodium linear alkylbenzene sulphonate (NaLAS) is the usual surfactant present in high foam laundry detergents. The foam behaviour of NaLAS is significantly dependent upon the foam generation methodology, water hardness and the antifoam action of deterged sebum soils. Here a study of the foam behaviour of NaLAS (and C12 4-phenyl SO3Na) solutions at different Ca2+ concentrations and pHs in the absence and presence of antifoam is presented. Two foam generation methodologies were used - tumbling tube rotation and cylinder shaking. It has been found that these two methodologies correlate well with a coefficient of ≥ 0.95 when comparing foamabilities. The correlation coefficient however declines to ~0.82 when comparing foam stabilities. The reason of this deterioration has been attributed to the differences of antifoam effect in foam films after foam generation due to differences in bubble size distribution formed by these two methodologies. In the absence of antifoam, the foam behaviour is independent of pH and is dominated by the formation of Ca(LAS)2 (or Ca(C12 4-phenyl SO3)2 lamellar phase liquid crystals. Dynamic surface tension measurements confirm that low foamability after the micellar-precipitate boundary of the Ca2+-LAS- (or Ca2+- C12 4-phenyl SO3-) precipitation phase diagram is due to low rates of transport of surfactant to the rapidly expanded air-water surfaces. Mixtures of triolein/stearic acid and triolein/tristearin are used as models for sebum soil antifoam, as they show similar antifoam effects regardless of pH and calcium concentration. In these two systems, crystalline particles are always present provided, in the case of triolein/stearic acid, formation of soaps is suppressed at low pH. Both stearic acid and tristearin particles adopt an oil-water contact angle >OW > 90° measured through the aqueous phase. They invert the O/W emulsion behaviour shown by triolein alone to W/O by rupturing the oil-water-oil emulsion films. They will also rupture the air-water-oil pseudoemulsion films provided the conditions of θAW > 2.6° for stearic acid and θAW > 0o for tristearin are satisfied. This behaviour of particles will facilitate the emergence of triolein droplets into air-water surfaces. Foam film rupture however only occurs under dynamic conditions, where bridging coefficients for triolein are expected to be positive. However under the near-equilibrium conditions prevailing during foam stability, bridging coefficients for triolein are negative. Little or no antifoam activity is therefore observed under those conditions with these triolein-based mixtures. Oil/particle mixed antifoams probably deactivate through a splitting and coalescence process. Triolein/stearic acid antifoam deactivates more rapidly than sebum soil and triolein/tristearin. This is mainly caused by formation of large inactive agglomerates which occurs both after antifoam dispersion and after continuous foam generation.

Overbased detergents are oil additives, which are included in oil to neutralise the acids that are generated as by-products during the combustion process within an engine. These overbased detergents have been investigated on an atomic scale by the preparation and characterisation of pure model complexes with relevant metal ions and ligands. Group 2 metal ion complexes have been prepared with sulfurised alkylphenol ligands from a range of conditions. The complexes prepared from methanol have shown that calcium cations and strontium cations give isostructural complexes and that the alkyl chain has a minimal effect on the structures of the complexes. In the solid state, the complexes all have the formula M₂L₂.6MeOH. Calix[8]arene complexes have been prepared, including a mixed metal ion complex with an ion-channel structure. Three calcium cation complexes have been prepared with calix[8]arene ligands, where two of the complexes are mimics for the precursors for overbased detergents as they contain calcium hydroxide cores. One of the complexes has a tetranuclear Ca₄(OH)₄ core and has shown that the conversion of the calcium hydroxide core to the calcium carbonate core in an overbased detergent is a facile reaction. The second precursor mimic contains a decanuclear calcium cation core and has the formula (Ca²+)₁₀(BC8⁵¯)₂ (OH)₈(OMe¯)₂(DMF)₁₀.5DMF. An unusual monodentate carboxylic acid complex with calcium has been prepared which utilised ligand design to achieve the desired monodentate coordination. Finally, a novel complex containing calcium cations and carbonate anions has been prepared, which has the formula Ca₁₀(M2²)₈ (CO₃²¯)₂(DMPD)₄(MeOH)₄.8acetone. This complex contains µ₆-CO₃²¯ anions and can be considered to be a model for overbased detergents.

La balance hydrophile-lipophile de tensioactifs et l‘hydrophobe de la phase huileuse sont des paramètres cruciaux dans la formulation des émulsions et des microémulsions. L'influence de l'addition d'alcools, des matières premières de parfumerie et d'agents tensioactifs sur la température d'inversion de phase (PIT) d'une émulsion de référence C10E4/octane/eau (fw = 0,5) a été étudiée. Les tensioactifs purs du type alcool polyéthoxylés (CiEj) montrent une variation linéaire de la PIT avec la fraction molaire x2 et peuvent être utilisées comme standards pour calibrer une échelle en termes de la pente dPIT/dx2. Ce paramètre conduit à une classification simple des tensioactifs par rapport au C10E4. Les valeurs positives et négatives correspondent à des tensioactifs plus ou moins hydrophiles par rapport au C10E4, respectivement. La comparaison des tensioactifs ioniques et non-ioniques ayant la même chaîne dodécyle permet le classement de différentes têtes hydrophiles. Plusieurs tensioactifs utilisés dans l‘industrie cosmétique, pharmaceutique et alimentaire et de nouveaux tensioactifs biosourcés ont été étudiés. Pour évaluer l‘hydrophobie des esters, une approche différente est utilisée en étudiant le comportement de phase des systèmes C10E4/ester/eau. Quinze esters ont été étudiées et leurs nombre de carbone équivalent (EACN) ont été déterminées à partir de la température T*de la queue du diagramme de fish. L'influence de la structure chimique des monoesters sur l'EACN a été rationalisé en termes la position du groupe ester et le nombre total de carbone, et s'explique par l'influence de ces huiles sur le paramètre d‘empilement "effectif" dans la couche interfaciale. / The hydrophilic-lipophilic balance of surfactants and the hydrophobicity of the oil phase are key factors in the formulation of emulsions and microemulsions. The influence of the addition of alcohols, some perfumery raw materials and surfactants on the phase inversion temperature (PIT) of a reference C10E4/n-octane/water emulsion (fw = 0,5) has been studied. Well-defined polyethoxylated alkyl surfactants (CiEj) show a linear variation of the PIT with their molar fraction x2 and can be used as standards to calibrate a scale in terms of the slope dPIT/dx2. This parameter leads to a simple classification of surfactants with respect to C10E4. Positive and negative values correspond to more or less hydrophilic surfactants compared to C10E4, respectively. The comparison of various ionic and non-ionic surfactants having the same dodecyl chain tail allows ranking the polar head hydrophilicity. Several industrial surfactants used in cosmetic, pharmaceutical and food industries and new bio-based surfactants were investigated. In order to class esters oils, a different approach based on the phase behavior of C10E4/ester oil/water systems was developed. Fifteen ester oils were studied and their Equivalent Alkane Carbon Numbers (EACNs) were determined from the so-called fish-tail temperature T* of the fish diagrams. The influence of the chemical structure of linear monoester on EACN was quantitatively rationalized in terms of ester bonds position and total carbon number, and explained by the influence of these polar oils on the "effective" packing parameter of the interfacial layer.