2008 Surfactants and Detergents
S&D 1.1: New Trends in Fabric Care
Chair(s): J. Pytel, Stepan Co, USA; and M.O. Dery, Akzo Nobel Surface Chemistry, USA
The Influence of Wash Conditions on Stain Removal. S.T. Adamy, F.R. Cala, Church & Dwight Co., Inc., Princeton, NJ, USA
Results of a series of studies on the influence of various wash conditions on the removal of certain stain types is presented. Detergency studies on cotton and polyester cotton were performed using both hydrophobic and hydrophilic stains in simple wash solutions via a Terg-o-tometer. Studies initially focused on buffered systems containing no surfactant and no degree of hardness in order to determine the influence of pH. Studies were then continued with increasing degrees of complexity in order to assess additional influences. These influences included water hardness, presence of chelating agents, and the addition of various cleaning adjuncts.
The Influence of Alcohol Structure on Cold-Water Cleaning Performance. W. Schmidt1, E. Endler1, K. Raney1, V. Jud1, C. Robles1, J. Barnes2, 1Shell Global Solutions (US) Inc., Houston, TX, USA, 2Shell Global Solutions Inc., Amsterdam, The Netherlands
With continued emphasis on efficient use of all resources, detergency with prototype liquid formulations has been evaluated at room temperature. Liquid formulations have been emphasized, as this product has become highly preferred in many countries. Selected formulations containing alcohol ethoxylate, alcohol ethoxysulfate and / or linear alkylbenzene sulfonate provide excellent detergency. Cleaning was evaluated with laboratory radiotracer methods, but also using standard reflectance stains in a washing machine. Limited experiments with prototype laundry powders have additionally displayed excellent cleaning. Alcohols were evaluated which were > 99% linear and < 50% linear. Low temperature detergency was enhanced by the use of 20% branched alcohol hydrophobes. Formulation stability, that is, phase stability at reduced storage temperatures, is enhanced by alcohol structures that are 20% branched.
Method for Predicting Enzyme Storage Stability in Liquid Surfactant Systems. D. Winetzky, L. Wallace, Genencor, A Danisco Division, Palo Alto, CA, USA
The determination of enzyme stability in detergents typically takes a significant amount of time. Differential Scanning Calorimetry (DSC) measures the melting point of proteins, and it can be used to predict the thermal stabilty of enzymes in liquid surfactant systems. Results show a good correlation between melting point (Tm) measurements on the DSC and storage stability results. DSC can also be used to predict the effects of formulation ingredients on enzyme stability. The development of a quick screening tool to predict the thermal storage stability of enzymes in liquid surfactant systems would save valuable product development time and result in more stable products.
Cationics for Through-the-Wash Softening. M. Dery, Akzo Nobel, Brewster, NY, USA
It has long been a goal of the industry to formulate laundry detergent compositions that have good cleaning properties together with textile softening properties thereby avoiding the use of a separate rinse-added textile softener product in addition to the usual laundry detergent. Such products are often referred to as 2-in-1 laundry detergents or "softergents". Since cleaning by definition involves the removal of unwanted material from the textile surface and textile softening normally involves deposition of softening agent onto the same surface, this technology requires that a balance be reached between the cleaning and softening performance. Cationic surfactants have long been known as useful additives in laundry detergent compositions for the purpose of providing laundered textiles with a softening, static control and/or sanitization benefit. The performance of a new class of quaternary ammonium compounds is reviewed in this presentation. The performance benefit of these compounds is quantified. A structure activity correlation is presented comparing performance vs traditional monoalkyl quaternaries. Finally, a mechanism is postulated to explain the unexpected softening benefit.
Wet Dryer Sheets. M. Doerr1, R. Wachter2, S. Gross1, C. Sturm2, A. Kvecher1, 1Cognis Corp., Ambler, PA, USA, 2Cognis Deutschland GmbH, Duesseldorf, NRW, Germany
Wet Dryer Sheets are a novel tool to transfer fabric softeners and other substances onto fabrics during tumble drying. Unlike liquid fabric softeners the chemicals need not to carry a cationic charge because the transfer to fabrics is diffusion controlled, and unlike regular dryer sheets, the distribution takes place equally throughout all fabrics. This novel transfer mechanism opens the door for the application of other components like UV absorbers, odor absorbers or insect repellents, which give special protection to the fabric. In case of fabric softening, components can be added which circumvent typical softener disadvantages, like greasy feel or water repellency. Additionally, skin treating products can be added like emollients, lotions, or compounds for moisture retention. During the wear of the fabrics these components are released to the skin, and deliver the desired benefits. In the presentation two products, one for fabric, and one for skin treatment are presented.
A New Additive for Laundry Detergents for Enhanced Fabric Softening and Fragrance Retention. A. Sengupta1, M. Hughes2, 1AMCOL Detergent Specialties, Arlington Heights, IL, USA, 2AMCOL Detergent Specialties, Winsford, Cheshire, UK
Two of the most popular consumer demands for a laundry detergent product are long-lasting fragrance and softening effects delivered through the wash, but all whilst maintaining good cleaning. Delivering these benefits through detergent products at a level of adequately meeting consumer expectations, continues to be challenge for product formulators. This is because i) the detersive action of surfactants prevents adequate deposition of these benefit agents onto the fabric, ii) rapid evaporative losses of fragrances. A new additive for detergents is designed to address these two problems by enhancing the deposition of hydrophobic benefit agents onto substrates being washed, while providing a mechanism for minimizing rapid dissipation of fragrances. The benefit agents are packed into a suitably modified oil phase, albeit using no waxes, to minimize the evaporative losses of fragrances. The oil phase is then emulsified in the form of an oil-in-water emulsion using a multicomponent cationic emulsifier system which serves as a deposition aid. The close association between the emulsifier and the benefit agent-laden oil phase boosts the deposition efficiency. This technology can also simultaneous deliver multiple benefit agents. The present paper will feature the technology and its performance properties.
Novel Features of a Fabric Styling Agent and Their Mechanisms. A. Ishikawa, S. Inoue, A. Fujiu, N. Yamaguchi, M. Tsumadori, Kao Corporation, Wakayama, Japan
Needs for wrinkle reduction and shape retention on fabric care application have been increasing. Typically silicones have been formulated for these purposes, however, most products could not restore original shape in clothes by a single process.As an approach to meet both functions, we discovered the novel microscopic behaviors of double-layered structures on fibers, which are derived from the combined application of a fiber lubricant and a fiber reinforcer.The key point in building such a double-layered structure was to have practically no miscibility in each, molecularly. Due to this physicochemical nature, these substances provided both targeted functions without sacrificing any of each functional advantage. As a result, we learned that the best combination is a specific silicone as a lubricant and nonionic polymer as a reinforcer.The microscopic analyses, such as TOF-SIMS, AFM and XPS, on the surface of fibers applied with these two substances revealed that the reinforcer molecules are absorbed directly on fibers and the lubricant molecules are absorbed onto the reinforcer molecule layer, respectively. It is speculated that the inner layer can reinforce fibers to help maintain the original shapes and the outer layer can effectively decrease the interfiber friction to reduce wrinkles and to de-stress fibers so as to restore original shapes.
Methodology for Rapid Reformulation of Greener Cleaners. M. Busby, P. Varineau, K. Weber, Dow Chemical, Midland, MI 48674
There is a drive to change cleaner formulations due to pressure from environmental regulations, labeling laws, and greater awareness of environmental issues by consumers. Making stable formulations with new raw materials can be a lengthy process. The range of actives available for cleaner formulations is very large, but the use of computer modeling can help formulators to select promising environmentally friendly ingredients based on the requirements of the cleaners. Computer modeling for formulation development and rapid formulation tools to prepare samples and screen physical properties and cleaning performance has been used to quickly optimize formulations. These tools have been applied to hard and soft surface cleaners resulting in significantly reduced cycle time, more efficient use of human resources, and reduced waste generation. The large volume of data produced by these methods allows the generation of predictive models which can further improve the reformulation process.
Rheology Modifiers for Detergents and Cleaners. J. Jefferis, BASF - Care Chemicals, Wyandotte, MI, USA
Rheology modifiers play an important role in detergents and cleaners. They allow the formulator to regulate the fluidity of the final formulation which allows for controlled dosing by the consumer or for specialized dosing by dosing units in industrial applications. In addition, modifying the rheology translates into enhanced performance through the ability to suspend actives, increase the contact time between actives and soils (especially on vertical applications), and can influence foam behavior. The current presentation will describe rheology modifiers developed specifically for detergents and cleaners. The performance attributes will be discussed within relevant formulation conditions and in the context of general rheology phenomenon.
S&D 1: General Surfactants I
Chair(s): R. Bernhardt, Stepan Co., USA; and G. Dado, Stepan Co., USA
Determination of the Critical Micelle Concentration of a Surfactant in the Presence of Surfactant-Adsorbing Particulates. Brian Grady, Andrew Carswell, Aaron Lowe, University of Oklahoma, Norman, OK 73069, USA
An efficient method for determining the critical micelle concentration (CMC) of surfactants in the presence of micron-sized surfactant adsorbing particulates via the utilization of ultrafiltration membranes is presented. The capabilities and limitations of this method to measure free surfactant concentration both above and below the CMC are explored and discussed. This method was used to determine the CMC of sodium dodecyl sulfate (SDS) in the presence of aluminum oxide and titanium dioxide. For both substrates, the CMC corresponded to the turning point of the adsorption isotherm, far below the CMC measured without the solid substrate. This reduction in CMC was attributed to excess sodium ions in solution, indicating that metal cations at the solid surface were able to neutralize the dodecyl sulfate anion. This agreement between the CMC and the turning point of the isotherm may indicate that adsorption halts because micelles form; however, the surface might still be saturated with surfactant if surface saturation coincides with the CMC.
APE Alternatives Based on Alcohol Ethoxylates. M.A. Sharp, K.L. Matheson, K.D. Sharp, Sasol North America Inc., Westlake, LA, USA
Alkylphenol ethoxylates (APEOs) have historically been the workhorse nonionic surfactants in several market applications due to their ease of handling, their formulation versatility, and their good performance. However, recent market concerns have prompted interest by formulators to look for effective alternatives to APEOs. During the last few years this pressure has already resulted in the replacement of most of the nonylphenol ethoxylate (NPE) consumed in household detergent applications in North America. In selecting APEO alternatives it is important to consider the performance of the alternative nonionic surfactants and their volume availability. Alcohol ethoxylates represent a large volume, diverse class of nonionic surfactants which vary widely in alkyl chain length, alkyl chain structure, weight percent ethylene oxide (EO) level, and distribution of EO adducts. The purpose for this paper is to assist the formulator in that selection by providing more information on comparing AEs with APEOs. In particular, branching and isomeric diversity in the alkyl chain and a narrow distribution of EO adducts are desirable structural characteristics for preparing alcohol ethoxylates with performance equivalent to APEOs.
Kinetics of Precipitation of Mixtures of Anionic Surfactants. J.F. Scamehorn, S. Soontravanich, University of Oklahoma, Norman, OK, USA
The overall time required for calcium-induced precipitation of mixed sodium dodecyl sulfate (SDS) and sodium octylbenzene sulfonate (SOBS) over a particular range of ratios has been found to increase dramatically when compared to either SDS or SOBS alone. In this study, light transmission and isoperibol calorimetry were used to measure the delay in the precipitation reaction. Scanning electron and optical micrographs of crystals formed give insight into the mechanism of synergism of mixtures. The smaller the difference in the supersaturation ratio of the two precipitating surfactants, the longer the induction time is. The delay in the extent of precipitation is due to the interruption of crystal formation from dissimilar precipitating surfactants and the reduction in the supersaturation when mixtures of surfactants are used.
Nonionic Surfactants in Solvent Replacement. E.R. Theiner, C.L. Dollar, K. Yacoub, J.M. Shabrach, Air Products and Chemicals, Allentown, PA, USA
Solvents are used in HI&I cleaning to overcome interactions within the soil and to allow surfactants to penetrate these soils. Unfortunately, most solvents are hazardous in one way or another including typically being volatile organic compounds. New developments within the area of nonionic surfactant research has developed a model by which the behavior of solvents may be mimicked yet retain the relatively benign characteristics of these surfactants.
Alcohol Ethoxylates as Replacements for Nonylphenol Ethoxylates. B. White, E. Endler, Shell Global Solutions (US) Inc., Houston, TX, USA
As an alternative to nonylphenol ethoxylates, alcohol ethoxylates (AEs) can be utilized because of their superior biodegradability, well-understood ecotoxicity, and lack of endocrine effects. In general, replacement options are dependent upon the specific application and properties required. AEs based on C9-C11 hydrophobes (AE 91) do not gel, wet faster, and yield less color in the presence of caustic media than NPEs. These attributes allow for industrial and institutional products to be formulated easier, offer faster penetration, and discolor less. AEs based on C12-C15 hydrophobes with nine moles of ethylene oxide (AE 25-9) biodegrade faster and more completely than a nine-mole octylphenol ethoxylate (OPE-9) as determined by primary and ultimate biodegradation laboratory tests. A range of AEs from AE 91-6 to AE 1-9 is appropriate for wetting applications depending on the requirements of the application. AE 91-6 enters solution almost immediately, while AE 91-8 and AE 1-5 most closely resemble the solution time of NPE-9. Alcohol ethoxylates offer greater formulation ease at up to 40 wt% of surfactant in solution because gelling does not occur. Also, AEs offer the advantage of good wetting properties while maintaining good color stability under alkaline wet processing conditions.
Protein Purification Using 3-Phase Microemulsion Systems. Javier Gomez del Rio, Douglas G. Hayes, University of Tennessee, Knoxville, TN, USA
3-phase microemulsion systems consisting of mixed Aerosol-OT (AOT) / pH-degradable 1,3-dioxolane alkyl ethoxylate nonionic surfactant (CK)have been employed to isolate proteins. Proteins have been extracted into the middle phase of these systems at yields of >90%, driven by electrostatic or hydrophobic attractive forces between the enzyme surface and AOT, increasing the concentration of protein 5-fold. Appropriate microemulsion systems can be prepared by proper adjustment of the relative amounts of AOT and CK, the head group size distribution for CK, and the ionic strength, with the system formed at its hydrophilic-lipophilic balance temperature to facilitate rapid phase separation. The degree of success for forward protein extration and recovery of microemulsion-encapsulated proteins ("back-extraction") depends on the hydrophobicity of the protein, and on the procedure used to mix the microemulsion system components. Several schemes for back-extraction have been explored and will be compared.
Major New Developments in Chemical Regulation: North America and Beyond. Richard Sedlak, The Soap and Detergent Association, Washington, DC, USA
In August 2007, the Chiefs of State of the U.S., Canada and Mexico announced a major new initiative to accelerate the assessment and management of chemicals. This presents needed alternative to the European chemical regulation, REACH. The paper will address how this program will interact with REACH, the Canadian chemical management program and the Chemicals Dialogue of the Asia-Pacific Economic Cooperation forum.Oleochemical and detergent producers will need to be heavily engaged.
Ionic Surfactant Based on Alkylpolyglycoside. Adinath Mahadeo Ware1,2, S.A. Momin1, 1Institute of Chemical Technology, Mumbai, Maharahstra, India, 2Chemithon Engineers (P) Ltd., Mumbai, Maharashtra, India
Alkylpolyglycoside are non-ionic surfactants prepared on the basis of renewable raw materials. By utilizing D-glucose, probably the most common naturally organic monomer unit, as a surfactant base, the range of raw materials for surfactants is advantageously expanded. The development of new speciality surfactants based on alkyl polyglycosides is arousing considerable interest. The derivatization of alkyl polyglycosides is currently being pursued with great commitment.In this present work, sulfosuccinate derivative of APG was synthesized and studied for the surface-active properties like surface tension reduction, interfacial tension, foam stability, emulsifying power and wetting power. It was found that Sodium alkyl polyglycoside sulfosuccinate shows excellent improvement in surface-active properties than that of alkylpolyglycoside.
Mixtures of Cationic Surfactants and Amphoteric Surfactants as Multi-Functional Cleaners. Anand Upadhyaya, Nanofilm Ltd., Valley View, OH, USA
Cationic surfactants are used in a variety of applications as disinfectants, conditioners, antistats etc. However they provide poor cleaning property due to poor detergencies of quarternaries. In the present times there is a growing demand for multifunctional cleaners that will provide good cleaning property in addition to the primary function of a formulation (which could be as a biocide, disinfectant, conditioner etc.). In order to achieve this, in this work we have shown that select cationic surfactants can be mixed with select amphoteric surfactants, which are compatible and interact with quaternary ammonium salt, thereby enhancing the detergency while at the same time maintaining the desired property (antistatic etc.) of the quaternary. Statistical mixture design of experiments was used to find optimal ratios of cationic and amphoteric surfactants.
Production and Characterization of Novel Glycolipid Biosurfactants. T Fukuoka, T Morita, M Konishi, T Imura, D Kitamoto, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, Japan
Biosurfactants (BS) are amphiphilic compounds produced by a variety of microorganisms. They show unique properties compared to their chemical counterparts, such as mild production conditions, lower toxicity, higher biodegradability and versatile functionality. BS have thus been receiving increasing attention as environmentally advanced materials.Mannosylerythritol lipids (MELs), which are abundantly produced from vegetable oils by the strains of Pseudozyma yeasts, are one of the most promising glycolipid BS known. They consist of 4-O-beta-D-mannopyranosyl-erythritol as the hydrophilic group and fatty esters and/or acetyl groups as the hydrophobic moiety. MELs exhibit not only excellent interfacial and self-assembling properties but also various biological actions including antitumor and cell differentiation activities towards mammalian cells.We recently discovered novel types of MELs with different structures and interfacial properties. Here, we report the characterization and production conditions of the novel MELs.
S&D 2.1: Industrial Applications of Surfactants
Chair(s): M. Rosen, Brooklyn College, USA; and A. Aradi, Afton Chemicals, USA
Chemistry, Properties and Applications of Arylalkyl Sulfonic Acids and Their Derivatives. P.D. Berger, C.H. Lee, G. Cao, O.S. Hsu, Oil Chem Technologies, Inc., Sugar Land,TX, USA
Arylalkyl sulfonic acids are a new family of anionic surfactants that are produced through the reaction of an aromatic compound and an olefin sulfonic acid. This paper will present examples of the use of arylalkyl sulfonic acids and their salts as surfactants for several industrial applications including catalysts, asphalt additives, agricultural emusifiers and in oil recovery. Arylalkyl sulfonic acids have also been found to be excellent starting compounds for the manufacture of high molecular weight arylalkyl sulfonates, gemini sulfactants and arylalkyl ether sulfonates. Their ease of production, solubility characteristics and electrolyte tolerance make these products more effective and less costly anionic surfactants compared to alkylaryl sulfonates, alcohol ether sulfates and alpha-olefin sulfonates in many applications. The synthesis and properties of these new materials will be discussed along with applications such as the production of microemulsions for agriculture and pharmaceutical applications.
New and Novel Environmentally Safe, Biodegradable Green Solvents and Their Performance as Industrial Cleaners and in other Industrial Processes. David Fluck, Satyen Trivedi, Charlie Aymes, Joanne Iwanaga, Manilal Dahanayake , Rhodia Inc., Bristol, PA, USA
A new class of Green environmentally friendly biodegradable solvents have been developed and evaluated against traditionally used harmful solvents in metal cleaning and other industrial processes. These solvents meet CARB 310 regulations and well aligned with the Sustainable Green Chemistry principles. Derived from an optimized synergistic mixture of alkyl chains of glutarate, succinate and adipate diesters these novel solvents provide exceptional solvency, improved spreading, low interfacial tensions with enhanced wetting. In degreasing multitude of industrial soils, these solvents performed as effective substitute for traditionally used environmentally harmful solvents. Versatility of these solvents as industrial cleaners and in other industrial processes such as, coalescent agents in paints and coatings, foundry casting and coil/can coatings will be presented.
Surfactant Reduction Enabled by the Use of Isopropylnaphthalene Sulfonate Linkers. Philip Benes, Kim Friloux, Nease Corporation, USA
Water-soluble salts of isopropylnaphthalene sulfonates function as a single linker in cleaning compositions, while maintaining cleaning performance as compared with reference formulations. A methodology is provided for reformulating detergent compositions with isopropylnaphthalene sulfonate linker. This allows for a reduction in other raw materials such as anionic and nonionic surfactants, without additional lipophilic or hydrophilic linker, providing cost savings and environmental benefit.
Additives Interaction with Solid Surfaces Through Enhanced Surfactant Activity. A. Aradi, M. Meffert, T. Quinn, Afton Chemical Corporation, Richmond, VA, USA
Interaction of surfaces with additives in order to facilitate certain functions of those surfaces may be limited by a lack of compatibility between the additive medium and the surface being treated. The most convenient additive medium is liquid, either organic, or aqueous, or an emulsion of the two liquid phases. In most cases, the liquid medium serves as a carrier phase, within which the additive is either dissolved or suspended. When the additive medium is liquid, the texture of the surface being treated becomes an issue. Materials being treated may have surfaces that present a wide variety of textures, from smooth at one extreme, to porous at the other. In between one may find pattern texturing with shallow groves, all the way to very deep pores. The nature of texturing has a great influence on the ability of a liquid to wet that surface. Similarly is the chemical composition. Texturing affects surface wettability by influencing the contact angle a drop of that liquid makes with the surface. Surface texturing almost always inhibits wettability. The surface chemical makeup, on the other hand, affects wettability by providing functional groups that are either complementary, or physically antagonistic, to the chemical makeup of the liquid medium being used to wet that surface.
Highly Efficient Novel Viscoelastic Surfactants as Rheology Modifiers for Personal Care and Industrial Applications. Manilal Dahanayake, Kesavan Subramanium, Talingting-Pabalan Ruela, Gary Woodward, Modaressi Hedieh , Rhodia, Inc., Bristol, PA , USA
Utility of viscoelastic surfactants has significantly increased in industry with the discovery of certain long chain alkyl amidopropylbetaines that can provide high viscosity gels at concentrations, as low as 0.5 % by weight. In recent times these surfactants have been highly successful in replacing both natural hydrocolloids and synthetic polymers as rheology modifiers in various industrial applications. These amphoterics represent biodegradable, non-toxic and extremely mild class of surfactants. The zero shear viscosity of the surfactant solution shows rapid increase, by several orders of magnitude, at relatively low concentration above a critical value, C* that decreases as the chain length is increased. This behavior is consistent with the self-assembly of surfactant monomers into long rod shaped worm-like micelles. These zwitterionic surfactants show strong interactions with anionic and cationic surfactants with correspondingly higher viscosities and gel strengths indicating much more cohesive self-assembly for these binary surfactant systems. This paper describes the unique behavior of these surfactants in forming worm - like micelles and their influence on dynamic and static rheological properties in Personal Care and Industrial formulations/applications.
Various Roles of Surface Active Materials Used in Automatic Transmission Fluids. D Bell, Afton Chemical Corp., Richmond, VA, USA
Automatic transmission fluid contains numerous surface active components that are balanced to optimize shift performance. The surfactants include anti-foamants, seal swell agents, friction modifiers, detergents, dispersants, antiwear and extreme pressure agents, rust and corrosion inhibitors, and even viscosity index improvers if functionalized with polar groups. Some of these surface active components are mono-functional, but most are bi-functional or tri-functional. For example, metallic detergents and ashless dispersants not only assume the traditional role of keeping the transmission parts clean, but also modify frictional response. Functionalized polymers minimize lubricant viscosity change at elevated temperatures, keep the transmission parts clean, and modify the surface friction to affect shifting. The presentation will illustrate typical surfactant types and mechanisms of the roles each surface active component plays in automotive transmission fluids, as well as highlight new surfactants being developed to fulfill the increasing performance trends for next generation automatic transmission fluids.
S&D 2: General Surfactants II
Chair(s): F. Cala, Church & Dwight Co. Inc., USA; and S. Adamy, Church & Dwight Co. Inc., USA
Impact of Organic Solute Properties on Adsolubilization in Linker and Extended Surfactant Modified Alumina. Ampira Charoensaeng1, Sutha Khaodhiar2, David Sabatini3, 1The National Center of Excellence for Environmental and Hazardous Waste Management (NCE-EHWM), Chulalongkorn University, Bangkok, Thailand, 2Environmental Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand, 3School of Civil Engineering and Environmental Science, University of Oklahoma, Norman, OK, USA
A lipophilic linker system and an extended surfactant system are evaluated for making surfactant modified adsorbents. The lipophilic linker system used SDS and dodecanol while the extended surfactant system used an anionic surfactant which has a propylene oxide (PO) chain inserted between head and tail surfactant. The impacts of organic solute properties are evaluated through adsolubilization and solubilization of organic solutes with difference polarities, phenylethanol, ethylcyclohexane and styrene. The admicellar partition coefficient (Kadm) is used to quantity the adsolubilization capacity and, analogous to solubilization in micelles (Kmic), can be used to elucidate the locus of solubilization the surfactant micelles to palisade and core region of adsorbed admicelles. The surface characterization is investigated to admicelle formation with varying organic solute polarities on alumina surface. These results thus provide insights into external and internal linker-based and extended-surfactant-based admicellar systems and highlight the differences observed from admicelles based on conventional surfactant systems with the aim of enhancing the ability of surfactant-modified adsorbent for industrial and environmental applications.
Phase Behavior and Surface Characteristics in Terpene/Surfactant/Bicarbonate Systems. S.T. Adamy, Church & Dwight Co., Inc., Princeton, NJ, USA
This paper presents work on characterization of systems incorporating water, sodium dodecyl sulfate, glycol ether cosurfactants, terpenes, and sodium bicarbonate. Though a large body of work exists in the literature on similar systems containing sodium chloride and n-alkane type oils, little to no work has been focused on systems incorporating bicarbonate salt and terpene oil components. Investigations showed that the phase behaviors of these systems (with no terpene) were significantly affected by the presesence of sodium bicarbonate (compared with those employing sodium chloride referenced in the literature). Oil solubilization capacities were also affected by the terpene type. Results of surface tension and interfacial tension measurements are also discussed.
Effects of Polymerization on Admicellar Formation and Adsolubilization using Polymerizable Surfactants. Chodchanok Attaphong1, Sutha Khaodhiar2, David A. Sabatini3, 1National Center of excellent for Environmental and Hazardous Waste Management (NCE-EHWM), Chulalongkorn University, Bangkok, Thailand, 2Environmental Engineering, Chulalongkorn University, Bangkok, Thailand, 3School of Civil Engineering and Environmental Science, University of Oklahoma, Norman, OK, USA
One of the problems of using surfactant modified adsorbent is loss of surfactants from the adsorbent due to pH changes, dilution of surfactant concentration and/or desorption. In previous study, a bilayer of anionic polymerizable surfactants (Poly(oxy-1,2-ethanediyl), α-sulfo-ω-[4-nonyl-2-(1-propenyl)phenoxy]-, branched ammonium salts with 5 and 20 ethylene oxide (EO) groups) was adsorbed on the alumina, and then it was polymerized by UV irradiation with initiator. The desorption of polymerized surfactants was compared with non-polymerizable surfactant (Hitenol N 08). The results showed that the desorption of Hitenol N 08 both with and without irradiation were more than that of the polymerizable surfactants. Moreover, the result showed that increasing the number of EO group would decrease the polarity in palisade region and resulted in a reduction of the adsolubilized styrene. On the contrary, the adsolubilization capacity of ethylcyclohexane was reverse compared with that of styrene. In this study, the focus is on the desorption of polymerizable surfactants before and after irradiation. The results is expected that the desorption of the surfactants from the adsorbent surface should be reduced after irradiation. In addition, the effect of polymerization of polymerizable surfactants on adsolubilization capacity is evaluated.
Microemulsion-Based Detergency for Vegetable Oils: Low Energy and Water Consumption. T. Phan, D. Sabatini, University of Oklahoma, Norman, OK, USA
Triglycerides, the main components in vegetable oils, are very hydrophobic oils due to the unique structure of a bulky head and three long hydrocarbon chains. Thus, vegetable oils are among the most difficult oily soils to remove from fabrics. Surfactant systems that can remove vegetable oils effectively are of great interests. At the same time, with the trend towards environmentally friendly products, detergents that consume less energy and water are in great demand. The objective of this study is to formulate a microemulsion system for vegetable oil detergency that requires less energy and water than conventional detergents. Preliminary results show that extended surfactants combined with linkers can form microemulsion with canola oil at low salinity and produce IFT values below 0.1 mN/m. In our work, low temperature detergency was optimized in the Winsor Type II region which creates a chemical driving force to maximize surfactant adsorption at soil-bath intersurfaces with less mechanical forces required. Desorption of surfactants and oil removal will be driven by electrolyte concentration gradient in rinse water. Using this new formulation approach, vegetable oil detergency can be conducted under slightly agitated or soak-only conditions thereby requiring less water usage.
Innovative Approaches to Cleaning: High Throughput Screening Methods. A.G. Douglass1, D. Bendejacq2, O. Anthony2, R. Koetitz3, M. Joanicot3, 1Rhodia, Inc., Cranbury, NJ, USA, 2Rhodia, S.A., Aubervilliers, France, 3Rhodia LOF, Bordeaux, France
There is a continued need to identify new and improved chemistries and formulations that meet the demands of the marketplace. New fast screening methods have been developed and will be presented including the use of jet printing technology for minaturisation and automation of surface wetting and modification protocols. The results of these tests will also be presented and have helped identify breakthrough technologies such as for hydrophilisation and fast drying of plastic surfaces.
Proper Oleochemical Surfactant Selection in Formulating Highly Effective "Green" Hard Surface Cleaners. M. Ventura, M. Kouba, R. Ashley, S. Bolkan, Church & Dwight Co., Princeton, NJ, USA
The objective of this study was to investigate the correlation between cleaning efficiency and the interfacial properties and synergistic interactions among nonionic, anionic and cationic oleochemical-based surfactant mixtures in a heavy-duty hard surface cleaner composition. Recent changes in the marketplace have consumers demanding more sustainable products such as “green” cleaners. In many cases more conventional, petrochemical-based surfactants can not be incorporated into such cleaners regardless of their biodegradability or toxicity profiles. The cleaning efficiency of hard surface cleaners can be significantly improved by the proper selection and incorporation of oleochemical-based surfactants. Such an optimized mixture of surfactants can provide improved spreading, lower interfacial tension and enhanced detergency to a hard surface cleaner resulting in higher cleaning efficiencies. Receding and dynamic contact angles, spreading factors and hard surface cleaning efficiencies of various oleochemical-based surfactant mixtures will be presented.
High Throughput Formulation and Characterization of Water Soluble Polymer Surfactant Blends. C.J. Tucker1, K.A. Jurman2, A. Som3, C. Mohler1, 1The Dow Chemical Co., Midland, Mi, USA, 2The Dow Chemical Co., Boundbrook, NJ, USA, 3Dow Chemical International Pvt. Ltd., Pune, India
Aqueous solutions of water soluble polymers, such as cellulose ethers, are used in a wide variety of applications such as consumer cleaning products, personal care products and food products. While the phase behavior of cellulose ethers in water is well known there have been few systematic studies on the effect of added components (in particular different surfactant structures at higher concentrations) on the solubility and rheology of cellulose ether solutions. In this presentation we will describe an automated system for the preparation and characterization (solubility, presence of liquid crystalline phases and rheology) of complex aqueous systems consisting of water soluble polymers, surfactants, electrolytes and other solutes. This high throughput workflow allows one to prepare and characterize up to 3000 distinct formulations a day. We will share results describing the effect of surfactant structure and concentration on properties such as the lower critical solution temperature of various water soluble polymers and how this can help one understand the interactions between surfactants and polymers in solution.
S&D 3.1: Hard Surface Cleaning and Surface Modification
Chair(s): M. Robbins, Clorox Co., USA; and E. Szekeres, Clorox Services Co., USA
Novel Aqueous Fluorosurfactant-Polymer Complexes for Surface Modification. Mona Marie Knock1, Michael H. Robbins2, David R. Scheuing1, 1Clorox Services Company, Pleasanton, CA, USA, 2Clorox Services Company, Kennesaw, GA, USA
Water-soluble polymer-fluorosurfactant associative complexes were used for surface modification of glass. Treated glass was more hydrophobic and oleophobic than unmodified glass. The modified surface is also responsive to electrolyte: contact angles of brine differed significantly from those of water.
Characterization of Surfaces Modified with Novel Fluorosurfactant-Polymer Complexes. D.R. Scheuing1, M.M. Knock1, M.H. Robbins2, 1Clorox Services Co., Pleasanton, CA, USA, 2Clorox Services Co., Kennesaw, GA,USA
Complex formation between water-soluble polyelectrolytes and mixed micelles comprising nonionic surfactant and oligomeric ionic fluorosurfactants derived from fluorinated oxetane monomers was investigated. Polymer-micelle binding can be modulated via micelle charge density and/or electrolyte concentration. FT-IR can be used to characterize the adsorbed layers formed on Ge surfaces exposed to solutions containing the complexes. The adsorbed layers are found to contain fluorosurfactant and polymer, but lack nonionic surfactant.
Microemulsion Properties and Cleaning Efficiency of Extended Surfactant-Based Mixtures. A. Witthayapanyanon1,3, T. Phan2,3, J.H. Harwell1,3, D.A. Sabatini2,3, 1School of Chemical, Biological, and Materials Engineering, University of Oklahoma, Norman, OK, USA, 2School of Civil Engineering and Environmental Science, University of Oklahoma, Norman, OK, USA, 3Institute for Applied Surfactant Research, Norman, OK, USA
Microemulsions have proven to provide enhanced-cleaning power in many industrial applications. The low IFT and high solubilization potentials produced by microemulsions promote oil removal by the roll-up and snap-off mechanisms, resulting in cleaner substrates while requiring lower energy and mechanical input. In addition to the low IFT criteria, due to the dynamic nature of the cleaning process the kinetic of coalescence of microemulsion systems is notable for being a vital factor affecting cleaning performance. However, forming microemulsions with certain oils is a challenge. The key to success is the right surfactant selection. In this work, we demonstrate the dynamic interfacial properties and cleaning efficiency of synergistic mixtures of conventional and extended surfactants. The results show that a small blend of extended surfactants in the mixture can yield a dramatic IFT reduction for various oils, while the conventional surfactant helps speed up the coalescence rate of microemulsion drops. Moreover, the optimum formulation of these mixtures can be adjusted by varying the length of intermediate groups attached in extended surfactant molecules. Furthermore, we evaluate laundry tests as practical example of the cleaning effectiveness of these surfactant mixtures, and compare their result to a conventional surfactant formulation.
Mathematical Models to Predict the Solubilization of Hydrophobic Compounds in Hard Surface Cleaners. E. J. Acosta, University of Toronto, Toronto, Ontario, Canada
The solubilization of essential oils, such as limonene, in hard surface cleaners can be predicted if the "characteristic curvature" of the surfactant(s) and the "equivalent alkane carbon number" (EACN) of the oil are known. These parameters are used in a net-average curvature (NAC) model that predicts the composition of surfactant-oil-water systems in equilibrium. An example will be presented on the use of this model to predict the solubilization of limonene in a formulation produced with Aerosol-MA and electrolyte. Furthermore, it was found that the fraction of shortening removed from a glass surface is proportional to the solubilization capacity of the essential oil. In addition to this "equilibrium" solubilization model, the second part of this presentation touches on a mass transfer model that evaluates the kinetics of the cleaning process. This dynamic model shows that, in addition to the solubilization capacity of the essential oil, the surfactant concentration and the flow dynamics near the surface are determining factors of the cleaning performance. Finally, through the combination of the equilibrium and dynamic model, it is possible to define conditions where relatively low concentrations of essential oil and surfactant could yield similar cleaning performance to more concentrated products.
Designing Environmentally Preferable Degreasers. J. Wates, Akzo Nobel Surfactants, Brewster, New York, USA
As a result of many different driving forces, the use of greener cleaning formulations is growing rapidly. This paper will offer some ideas on how to design environmentally preferable degreasers that deliver the performance of more traditional systems. Most effective degreasers contain nonionic surfactant(s), hydrotropes, builders and optionally solvents. Each component will be considered in turn and approaches to selecting alternatives with lower environmental impact discussed. The aim is to identify how existing products can be improved environmentally while still meeting all performance targets, as well as satisfying local raw material requirements such as compliance with REACH in Europe.
S&D 3: Detergents that Clean and ...
Chair(s): P. He, Henkel, USA; and M. Hardin, Reckitt Benckiser North America, USA
Surfactants Influence Electrospinning of Chitosan–Poly(ethylene oxide) Blend Nanofibers. C. Kriegel1, K. Kit2, J. Weiss1, 1University of Massachusetts, Amherst, MA, USA, 2University of Tennessee, Knoxville, TN, USA
Polymer blends of chitosan ((1-4)-2-amino-2-deoxy-b-D-glucan) and poly(ethylene oxide) with a ratio of 3:1 were electrospun in 50% and 90% acetic acid to obtain nanofiber membranes at a flow rate of 0.02ml/min, an applied voltage of 20kV, a tip to target distance of 10cm and a temperature of 25ºC. To further broaden the processing window for nanofiber production, surfactants of different charge were added at various concentrations. The influence of viscosity, conductivity and surface tension on the morphology of the resulting nanofibers was investigated. Results show that with an increase in acetic acid concentration, conductivity and surface tension decreased and viscosity increased and surface tension was slightly reduced after addition of surfactants. During electrospinning of the mixed polymer solutions, ultrafine fibers with diameters from 40nm to 240nm were obtained. Pure chitosan did not form fibers, but was deposited as beads instead. However, addition of PEO and an increasing concentration of surfactants induced spinnability or yielded fibers of a larger diameter. Compositional analysis suggested that the nanofibers consisted of both polymers but more PEO was present in the fibers than in the original solutions. Thermal analysis revealed melting points characteristic for PEO and chitosan in all fiber samples.
Study on Enzyme Stability in Methyl Ester Sulfonate Solution. Megumu Ono, Yoshiyuki Hoshida, Masazumi Kikukawa, Lion Corporation, Edogawa-ku, Tokyo, Japan
In recent years, Methyl Ester Sulfonate (MES) has been getting a lot of worldwide attention as an environmentally-friendly surfactant which is derived from plant oil. In our previous reports we showed several of MES′s advantages as a laundry detergent such as it′s high detergency under low concentration and high tolerance to water hardness. Moreover, good compatibility with enzymes is another important property of MES. The activities of enzymes are maintained in the MES solution well, though they are often inactivated in some anionic surfactant solutions, such as Linear Alkyl benzene Sulfonate (LAS). To clarify the influence of MES in regards to the enzyme stability, we assessed the degree of denaturation of the protein in each anionic surfactant solution. We found that the denaturation of the protein caused by MES was less than that of LAS. We will report these experimental results and discuss the stabilization mechanism in detail.
Novel Amylase Enzyme for Detergent Applications. C. Choy1, Y. Kinoshita1, M. Goyal1, M.P.J. Deurzen2, P. Augustinus2, E. van Meerkerk2, L. Spaargaren2, Q. Westdijk-Patist2, 1Genencor, Division of Danisco, Applications, 925 Page Mill Road, Palo Alto, CA 94304, USA, 2Genencor International B.V., Applications and Technical Service Support, Leiden, The Netherlands
Amylases are commonly used in the detergent industry to facilitate the removal of starch-containing soils from fabrics and from dishes during the washing process. Current amylases in the market place lack the benefit of combining bleach stability and low dose response in stain removal. In this paper, we discuss the introduction of a novel detergent amylase that offers excellent stability in bleach-containing detergents and in high pH medium. The new amylase is also effective at low enzyme dosage, making it an efficient enzyme for applications in both laundry and automatic dishwashing. Stability and performance data of the novel amylase in both laundry and automatic dishwashing detergents compared with competitive benchmarks will be presented.
Effect of Ionic Head Group on Admicelle Formation of Polymerizable Surfactant. Emma Asnachinda1, Sutha Khaodhiar2, David A. Sabatini3, 1National Center of Excellence for Environmental and Hazardous Waste Management, Chulalongkorn University, Bangkok, Thailand, 2Environmental Engineering, Chulalongkorn University, Bangkok, Thailand, 3School of Civil Engineering and Environmental Science, University of Oklahoma, Norman, OK, USA.
One of the problems of using surfactant-modified adsorbents in surfactant-based adsorption process is the loss of surfactant during application. Recently, polymerizable surfactants have been use to minimize surfactant losses through polymerization of the surfactant admicellar structure to help fixate it to the solid oxide surface. For this study, the adsorption of polymerizable cationic gemini surfactant is used to form polymerized bilayers on silica oxide. UV light is used to irradiate and initiate the polymerization process. Surfactant adsorption and desorption are observed to compare the properties between polymerized surface of the gemini surfactant and non polymerized surfactant with the surface of conventional surfactant. The strong interaction of polymerized surface can enhance the dispersion stability and reduce desorption of surfactant from the surface and improve operating characteristics of the surfactant-modified media.
Multifunctional Detergents—More Than Just Washing the Laundry. Marc-Steffen Schiedel, Birgit Middelhauve, Henkel KGaA, Duesseldorf, Germany
Laundry detergents have to fulfill multiple consumer needs. It's more than removing stains. Overall cleanliness, anti-greying properties, color care and fiber protection are examples for additional benefits which have to be guaranteed, especially for high performing premium products. Furthermore new demands based on consumer's changing washing habits and lifestyles are coming along with functionalized textiles which are requesting innovative products. These products add value for the consumer by combining tailored surfactants, high effective builder systems, bespoken high performing additional ingredients and sophisticated fragrances to offer scent experiences and washing results that go beyond clean.In this work we will summarize today's market situations and give an outlook what might be in the pipeline for the consumer of tomorrow.
Surfactants: More Than Just A Way to Clean Clothes. S.E. Hecht, The Procter & Gamble Company, Cincinnati, OH, USA
It is widely known that surfactants play a critical role in consumer products, such as laundry detergents and cleaning products. Surfactants are also a key ingredient in personal care and baby care products, such as body wash, toothpaste, shave preparations, and baby wipes. Unlike the cleaning applications, the cleaning power of a surfactant is not the most important consideration for use in personal care products. Properties such as foaming, mildness, and aesthetics are much more important for these applications. This leads to a different selection of surfactants for use in personal care products.
Systematic Libraries of Block Co-Polymer Surfactants. P. McCarthy, N.V. Tsarevsky, W. Jakubowski, K. Matyjaszewski, ATRP Solutions, Inc., Pittsburgh, PA 15213, USA
Atom Transfer Radical Polymerization (ATRP) is one of the most powerful synthetic techniques that allows for synthesis of polymeric materials with predetermined molecular weight, composition, and molecular architecture derived from substituted styrenes, (meth)acrylates, or acrylonitrile. The polymers prepared by ATRP are chain end-functionalized and can be used as macroinitiators in chain extension reactions that yield block copolymers with excellent control over the segment size and nanophase separation. Block co-polymer synthesis requires careful study and optimization of various polymerization techniques and post-polymerization modifications. In this study, atom transfer radical polymerization (ATRP) was utilized to synthesize universal block copolymer precursors of non-ionic and ionic (both cationic and anionic) surfactants using styrene or hydrophobic methacrylates as the components of the hydrophobic segments, and glycidyl (meth)acrylate (GMA) as the hydrophilic segment precursor. The epoxide groups of GMA were reacted with nucleophiles to yield cationic (amine-based), anionic (phosphate-based) and non-ionic (alcohol-based) block co-polymer surfactants. Since each class of surfactant can be prepared from the same batch of parent block co-polymer, we consider this reactive block co-polymer to be a universal polymeric precursor.
Surfactant-Foam Study in Brine Solutions. D. Colovic, T. Germain, McIntyre Group, Ltd., University Park, IL, USA
A surfactant's ability to foam is not just a function of the surfactant but also the medium being foamed. The most familiar medium is water. Electrolytes are known to affect a surfactant's performance properties. Natural gas wells sometimes require the use of a surfactant to reduce hydrostatic pressure and lift water out of a well to improve production rates. The water in a well typically contains a significant amount of salts. Surfactants for this application therefore need to perform in brine water. This presentation will compare foam generation and water holding capacity of betaines, sultaines and other ampholyte surfactants in brine. Test data with and without petroleum hydrocarbon as a condensate equivalent will be shown.
S&D 4 / BIO 4.1: Bio based Surfactants
Chair(s): G. Smith, Huntsman Performance Products, USA; and D. Hayes, University of Tennessee, USA
Biosynthesis of Flavonoid Esters in Ionic Liquids. B.M. Lue, Z. Guo, X. Xu, BioCentrum, Technical University of Denmark, Kgs. Lyngby, Denmark
Room temperature ionic liquids (RTILs) are organic salts with low melting points and are often referred to as "green solvents" because they do not release volatiles into the atmosphere. RTILs are regarded as interesting substitutes for traditional organic media due to their high thermal stability, wide liquid range and potential for solubility modifications (through appropriate cation & anion selection).Flavonoids are widespread in foods and have been characterized by their anti-oxidative, anti-carcinogenic and antimicrobial properties. Unfortunately, flavonoids are not very soluble in hydrophobic environments and this limits their anti-oxidative efficiency. The acylation of flavonoids with fatty acids is of great interest as this would increase solubility of the flavonoids in the hydrophobic phase. These acylation products could then be employed as antioxidants or emulsifiers.Due largely to differences in solubilities, development of an efficient enzyme system for the acylation of flavonoids is problematic. The use of RTILs may potentially reduce or eliminate these difficulties through increased substrate solubility and the possible use of vacuum for removing water (i.e. due to lower vapour pressure), thereby increasing reaction efficiency, stability & perhaps specificity.This presentatoin will explore the use of various RTILs for the production of flavonoid esters.
Modified Vegetable Oils as Detergents and Emulsifiers. Raymond W. Cen, George A. Smith, Huntsman Corporation, HATC, 8600 Gosling Rd, The Woodlands, TX 77381, USA
We modified vegetable oils chemically via a proprietary G2 catalyst in Huntsman to form a group of ethoxylated vegetable oils (VEO). Several vegetable oils such as peanut oil, soy bean oil, canola oil, corn oil, and coconut oil can be easily ethoxylated through EO insertion to ester portion of triglycerides. Physiochemical properties as well as spectroscopic characterization were listed as function of EO stoichometry and oil identity. The application and efficacy for laundry detergents and other cleansing applications were shown. This group of bio-based detergents have tendency to form O/W emulsions even at oil:water ratio of 9:1 and beyond with good efficiency. Several examples of crowded O/W emulsions were also demonstrated here for their potential in different consumer goods application.
Kinetics Control of the Synthesis of Branched Hydrophobes from Oleochemicals. K.M. Doll1, S.Z. Erhan1, B.K. Sharma1,2, 1FIO, NCAUR, ARS, USDA, Peoria, IL, USA, 2Chemical Engineering, Pennsylvania State University, University Park, PA, USA
The synthesis of a series of branched hydroxy stearates from commercially available methyl oleate and common organic acids is reported. A variety of different acids, with 3 to 8 carbon atoms, and also varying in their branching and functionality, were used. The kinetics of the ring opening reaction was studied, under both pseudo 1st order conditions, and 2nd order conditions. An Arrhenius activation energy of 66.7 kJ mol-1 (16.0 kcal mol-1) was found in a system using propanoic acid as the ring opener. The resultant compounds have calculated molar volumes of ~375 cm3 making them a candidate for use as surfactant hydrophobes. The added oxygen groups and branched structures may allow the synthesis of improved surfactants from these materials as well. The general ease of the method should also allow its use with a variety of commercially available substrates, in order to obtain desired molecular structure. Finally, commercially available epoxidized soybean oil may also be modified by this method if a product with higher molecular weight is desired.
Formulation Design of Metalworking Fluid Microemulsions Using Bio-Based Surfactants. Fu Zhao1, Kim Hayes2, Steven Skerlos2, 1Purdue University, West Lafayette, IN, USA, 2University of Michigan, Ann Arbor, MI, USA
Metalworking fluids (MWFs) are ubiquitously used in the machine tool industry as coolants and lubricants. Conventional MWFs are based on petroleum feedstock, which result in high treatment and disposal costs. These factors along with increasing oil prices and the national security concerns associated with imported oil, serve as motivations to consider alternatives to petroleum-based MWFs. This paper presents a set of surfactant-selection guidelines that can be used to design bio-based MWF microemulsions. Nine classes (five anionic and four nonionic, with different head and tail structures) of bio-based surfactants are investigated for their capability to emulsify three representative vegetable base oils. Experimental results suggest that: a combination of two surfactants, one nonionic and one water soluble co-surfactant (either nonionic or anionic) is preferred over a single surfactant; the nonionic surfactant should have a carbon tail length greater or equal to the nominal carbon chain length of the fatty acids in the oil as well as a head group that is not excessively small or large (e.g., 10-20 ethylene oxide groups); the difference in tail lengths between the surfactant and the co-surfactant should be less than 6 to maximize the feasible range of oil to surfactant ratios yielding stable emulsions.
Extraction of Biosurfactants from Wastewater Biosolids: Challenges and Opportunities. F.Y. Garcia, D.G. Allen, S. Liu, E.J. Acosta, University of Toronto, Toronto, Ontario, Canada
This presentation describes the method of extraction and properties of a surface active materials extracted from activated sludge biosolids. While the composition of the extracted mixture is complex, its surface activity (CMC and surface tension after CMC) suggest that this material has similar properties to that of soaps derived from the saponification of lipids. Size exclusion chromatography, reverse phase - ion coupled chromatography, and interfacial tension data are presented in order to characterize the size, charge and hydrophobicity of the extracted material. Preliminary cleaning performance data and cytotoxicity studies will also be presented. The potential opportunities for these surface active materials and the challenges for their development into commercial products will be discussed.
Sugar Fatty Acid Esters and Alkyl Glucosides, Two Families of Enzymatically Prepared Biosurfactants in a Green Chemistry Perspective. A. Ducret, M. Trani, W. Levadoux, R. Lortie, Biotechnology Research Institute, National Research Council Canada, Montreal, Quebec, Canada
Sugar fatty acid esters and alkyl glucosides are two families of non-ionic biosurfactants having excellent surface-active properties (emulsifying, stabilizing, conditioning effects) making them suitable as ingredients in foods, detergents, therapeutic formulations, or personal care products. Enzymatically prepared from renewable resources (vegetable oils and carbohydrates) under mild conditions by direct condensation reactions (generating no by-products except water), they are completely biodegradable, and have a low environmental impact. Sugar esters are obtained by esterification of a sugar with fatty acid using a lipase while alkyl glucosides are obtained by condensation of a sugar and an alcohol using a glucosidase. In both cases, reactants (sugar and fatty acid or alcohol) are very poorly soluble in each other, limiting the productivity. The production of alkyl glucosides faces an additional challenge, the low tolerance of glucosidases to reaction conditions (low water activity, organic media). The experience of our lab on the synthesis of both families of biosurfactants and the approaches followed to overcome the hurdles mentioned above will be presented.
Bioreactor Design for the Solvent-Free Lipase-Catalysis of Saccharide-Fatty Acid Ester Biosurfactant. Sang-Hyun Pyo, Douglas G. Hayes, University of Tennessee, Knoxville, TN, USA
Bioreactor systems have been designed for the immobilized lipase-catalyzed synthesis of fatty acid-saccharide mono- and di-esters, which are useful biosurfactants and value-added products. The reactions were operated in the absence of solvent; moreover, the major technical bottleneck to overcoming the slow rate of reaction, the poor miscibility of the saccharide and acyl donor substrates, was addressed using the saccharide monoester product as a miscibility agent and an elevated temperature of 65 C. Two main reactor designs have been assembled and are compared. The first employs a packed bed containing saccharide and an adsorbent upstream of the bioreactor. The second involves introduction of saccharide through a suspension of crystalline saccharide powders into a fatty acid/monoester liquid mixture. Both systems were operated under continuous recirculation of reaction mixture through the bioreactor system. Although System 1 yields a lower saccharide solubilization compared to System 2, the latter of which produces micron-sized suspensions of crystalline saccharide, both provide similar time courses of esterification, converting a mixture of 20% ester / 80% fatty acid into 75-90% ester. The effect of operating parameters and water content are currently under exploration
Using Biosurfactant Mixtures to Form Microemulsions: Enhanced Solubilization and Potential Applications. T. Nguyen1,2, L. Do1,2, D. Sabatini1,2, 1University of Oklahoma, Norman, OK, USA, 2Institute of Applied Surfactant Research, Norman, OK, USA
Biosurfactant mixtures and biocompatible lipophilic linkers were used to form microemulsions with a wide range of oils. The biosurfactants studied are anionic rhamnolipids produced by microorganisms and nonionic methyl ester ethoxylates made from biorenewable feedstock of plants. Three different oils were studied: limonene, diesel, and vegetable oil. Due to the molecular structure of these surfactants and linker molecules, we hypothesize that these formulations can form alcohol-free and non-toxic microemulsions while achieving high solubilization capacity which is enhanced by using mixtures of biosurfactants versus single biosurfactants. These microemulsions can be used for various applications such as cosmetics, where an oil-in-water microemulsion is used, and vegetable oil extraction, where a water-in-oil microemulsion is used. We extensively study the vegetable oil extraction using water-in-oil microemulsion of diesel, which produces a blend of vegetable and diesel after the extraction. Various parameters such as surfactant concentration, salinity, and ratio of oilseed to liquid feedstock of the extraction process were evaluated for the effects on the ratio and viscosity of this vegetable oil â€“ diesel blends and their ability to be used as an alternative fuel to diesel and biodiesel.
Vegetable Oilseed Cake: Raw Material for Protein-Based Surfactants. Adinath Mahadeo Ware1,2, Sushilkumar Dubal1, S.A. Momin1, 1Institute of Chemical Technology, Mumbai University, Mumbai, Maharahstra, India, 2Chemithon Engineers (P) Ltd., Mumbai, Maharashtra, India
Synthesis of new surfactants with special functionalities are greatly needed to fine-tune existing surfactants for specific tasks. The raw materials cost, market size, energy needs, and health and environmental concerns have been the important factors especially for discovery and introduction of new surfactants. In this regard protein from oilseed cake, an agricultural byproduct abundantly available in the world, is one of the few major and economic sources of naturally occurring amino acid and can be regarded as a versatile and valuable raw material for surfactant production.Protein-based surfactants are usually synthesized with amino acids/peptides and fatty acids as building blocks. They are mainly of two types: peptide and amino acid surfactants. Both are interesting compounds that contain an amino or a peptide as the hydrophilic part and a long hydrocarbon chain as the hydrophobic portion. The hydrocarbon chain can be introduced through acyl, ester, amide, alkyl or ether linkage. Protein-based surfactants are usually considered biodegradable, nontoxic and nonirritating and, in some cases they have antimicrobial properties therefore they have great demand in cosmetics. The review deals with the utilization of oilseed cake in preparation of protein based surfactants and their applications in cosmetics and toiletries.
Novel Rinse Aid Microemulsions with Improved Biodegradability. Andras Nagy, Saiid Mohammed, Dennis Parrish, Janet Kosiek, Georg Schick, Goldschmidt Chemical Corporation, Hopewell, VA, USA
Conventional rinse aids/drying agents consist of an emulsifier, a hydrophobe, a coemulsifier and water. Most ingredients are not biodegradable according to OECD methods and can have other undesirable effects and characteristics.This paper defines novel rinse aids with improved biodegradability and more desirable environmental and performance profiles. Traditional ingredients are replaced with more biodegradable, environmental friendly ones: dialkyl dimethyl quaternary ammonium emulsifiers are replaced with ester quaternaries, mineral seal oil hydrophobes with ester oils, flammable solvents and co-emulsifiers with non-flammable ones. The resulting microemulsion rinse aids are clear or translucent, easily dilutable even with cold water, will not go through viscous gel phases, have favorable performance characteristics in terms of beading and sheeting and are compatible with other performance and aesthetic enhancing additives like organo- modified silicones, dyes, perfumes, etc. Test methods and advantages will be presented.
Interfacial Properties of Sugar-Based Surfactants and Their Applications. P. Somasundaran, S. Lu, J. Wu, P. He, Columbia University, New York, New York, USA
The interfacial properties of surfactants play a critical role in determining their performance in many industrial applications, such as detergency, enhanced oil recovery and water treatment. Due to the increasing demand for environmental friendly reagents, green surfactants have received considerable attention recently. The unique surface activity and biodegradability make this group of surfactant become the candidates for the next generation reagents. In this work, the interfacial properties of sugar based alkyl glycosides and sophorolipid esters were investigated. These surfactants show high surface activity and salt tolerance. When mixed with conventional surfactants including anionic, nonionic and cationic, the system exhibit nonideal mixing suggesting synergistic interactions. In addition, sugar based surfactant, n-dodecyl-β-D-maltoside, was found to have high selectivity of adsorption on oxide minerals. For instance, it adsorbs on alumina, titania and hematite but not on silica. The mechanism has been successfully revealed by correlating the adsorption to the solid surface species concentrations. The wettability of the substrate surfaces was found to change significantly with the adsorption. Furthermore, this sugar based surfactant was successfully applied to separate a model pollutant, phenol, from aqueous solutions using micellar enhanced ultrafiltration. The performance of the surfactant was found to be governed by the intermolecular interaction and the nanostructure of the surfactant micelles. Undoubtedly sugar based surfactants will have a potential impact on the chemical evolution of the down-stream industries and this study will promote the application of these environmentally friendly surfactants.
Surfactants & Detergents Posters
Chair(s): C. Choy, Danisco USA Inc., USA
Going for the Green: Formulating with Natural-Based Alcohol Ethoxylates.
K. Kennedy1, J. Shabrach1, K. Yacoub1, A. Sun1, E. Theiner1, C. Dollar2, B. Swenson2, 1Air Products and Chemicals, Inc, Allentown, PA, USA, 2Air Products and Chemicals, Inc, Milton, WI, USA
Sellers of commercial cleaners are constantly looking for new ways to stay competitive and differentiate themselves from their competition. In recent years, there has been a pull from the marketplace to demand cleaners with good performance and reduced environmental impact. In 2006, Wal-Mart and others started a movement by requiring its suppliers to rid their formulations of NPEs and provide "greener" formulations. Use of naturally-derived materials is one way that the industry is responding to this move towards "green" products. This paper will detail the challenges and rewards to using naturally-derived surfactants in formulations for I&I cleaning. Discussion will be given to the considerations needed to overcome seemingly limiting characteristics of these materials. Finally, examples of formulations useful in I&I cleaning will be presented.
Synthetic Approaches for Preparation of Systematic Polymeric Surfactant Libraries.
P. McCarthy, W. Jakubowski, N.V. Tsarevsky, K. Matyjaszewski, ATRP Solutions, Inc., Pittsburgh, PA 15213
Over the last decade, block co-polymer surfactants have attracted increased interest due to their unique ability to assemble into ordered nano-scale structures. To utilize these materials, it is important to establish relationships between polymer structure and physical properties. These correlations can be difficult due to sample-to-sample variability. For instance, each block in a block co-polymer can have different molecular weight, polydispersity, and composition. Here we describe two synthetic approaches which yield systematic libraries of block co-polymers by atom transfer radical polymerization, the macroinitiator approach and the universal precursor approach. The macroinitiator approach yields block co-polymers with the same first block and varying second blocks. This approach can be used to generate systematic libraries where only one of the blocks has varying molecular weight and/or polydispersity. The universal precursor approach utilizes a reactive block which upon transformation, yields systematic libraries of block copolymers where only composition varies while molecular weight and polydispersity of both of the blocks remains constant. We show several examples of how systematic libraries of block co-polymers can be generated by both the macroinitiator approach and the universal precursor approach.