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D ET E RG E N TSS U R FAC TA N TS

H.G. Hauthal*

CESIO 2004 – Dynamic Surfactants and Nanostructured Surfaces for an Innovative Industry

Keywords: Surfactants, detergents, raw materials, oleochemicals, GTL technology, industrial application,emulsifiers, personal care, nanostructured surfaces, environment, ecology, legislation, wellness, sustainable development, market data

The World Surfactants Congresscame back to Germany: Afterthe first CESIO event in 1984

in Munich the 6th CESIO Congress‘Surfactants make the world goround‘ took place in Berlin andaround 1000 people attended thishigh-level meeting perfectly orga-nized by TEGEWA and its formerchairman of many years, LotharNoll. Besides eight Plenary Lec-tures in five Sections A – Raw Ma-terials and Processing, B – Struc-tures and Properties, C – IndustrialApplications, D – Household, I & Iand Personal Care, and E – Envi-ronment, Toxicology and Regula-tory Affairs 100 oral presentationswere given. The scientific programwas rounded up by more than 110posters. The exhibition offered abroad forum for initiating, renew-ing, and strengthening of personalcontacts.The 6th CESIO Congress wasopened by Arno H. Stegk, Presi-dent of CESIO, who also chairedthe Plenary Lectures.

Introduction

Instead of the EU Enterprise Commission-er E. Liikanen some remarks on »Shapinga Competitive Environment for EuropeanIndustry« were given by P. Hennessy, Di-rector, »Environmental Aspects of Enter-prise Policy, Resource-based and SpecificIndustries«, EU Directorate General En-terprise. Three steps are necessary to ad-dress the new challenges including theEU enlargement: Ensuring that indus-try is not overburdened with regulation,making sure that all the EU policies helpto reinforce industrial competitiveness,and developing the sectoral dimensionof industrial policy. »... we not only needa healthy environment for a healthyeconomy; we also need a healthy econ-omy for a healthy environment«, he said.»The Challenge for Our Industry: Chang-ing World Demographics« was analyzed byS. van Straelen in another Plenary Lecturethat also highlighted new ways to engagethe consumer.

The Global Surfactant Market

The global surfactant market volume sizeis about 12 million tons (2003), with anoverall rough value of 13 billion Euro.The regional split shows North Americato be the biggest surfactant market inthe world with 35%. Asia-Pacific followsnext with 29%, Western Europe con-sumes 23%, the rest of the world ac-counts in value for 13%. The split of theglobal surfactant market by end-userapplication is shown in Fig. 1, by suppli-ers in Fig. 2.The global household detergent markethad a value in 2002 of 29 billion Euro.

Framework Conditions for aSustainable Chemical Industry

The chemical industry is one of the topindustries in 11 of the former 15 EU mem-ber states. With an employment of 1.7million (plus 3 million indirectly) sales of528 billion Euro (with pharmaceuticals)were achieved in 2002. The trade surplusamounted to 70 billion Euro. Against thisbackground E. Voscherau, Vice Chairmanof BASF and President of CEFIC, asked inhis Plenary Lecture for better »Frame-work Conditions for a Sustainable Chemi-cal Industry in Europe«. His policy recom-mendations are

• Go for the Lisbon goal and make Eu-rope the most dynamic knowledge-based region in the world by 2010!

• Establish a new industrial policy to im-prove competitiveness without inter-ventional measures (chemicals policyas a test case).

• Create a climate that promotes inno-vation.

• Orientate environmental legislationtowards sustainable development andgive equal weight to all three aspects –environmental, social and economic.

• Avoid regulatory solo-runs in Europe.

• Deliver less bureaucracy and better(not more) regulation.

• Use the most efficient and cost-effec-tive means to achieve environmentalgoals.

• Base political decisions on sound sci-ence.

6T H WORLD SURFAC TA N TS CO N G R E SSS U R FAC TA N TS

Just three global players together domi-nate 62% of the market (P&G – 29,Unilever – 22, and Henkel incl. Dial 11%).Reckitt Benckiser and Colgate with 3%each of this market are much smaller butactive in many countries.After presenting these data U. Lehner,Henkel KGaA, in his Plenary Lecture dis-cussed »Surfactants Surfing Around theWorld – Requirements for the Surfac-tants Industry – The Market Partners‘Point of View«. Clustering the demandsfrom consumers in three different claimdimensions for the product segment ofheavy-duty detergents results in per-formance, convenience, and aesthetics.These future demands can only be solvedin a close cooperation between suppliersand manufacturers. Product cycles aregetting shorter and shorter because in-novations are more rapidly copied, fore-most by private labels. Striving for inno-vation within the economic boundariesis difficult enough but additionally, thereis a growing number of laws, regulations,and directives (European Detergents Regu-lation, Biocidal Products Directive, Dan-gerous Preparation Directive).The consumer expectations in the emerg-ing countries of South America, Africa,and Asia are more basic than in Westerncountries but include clear performanceexpectations for household detergents.Because the washing machine penetra-tion is very low, for instance, only 15%in India compared to 95% in Germanyquality perceptions such as good foam

characteristics, skin compatibility as wellas pleasant perfume are important fordetergents. A general development formany emerging markets is the replace-ment of soap and detergent bars by pow-der detergents that are twice as expen-sive. Fig. 3 shows the future demands forsurfactants in Asia-Pacific compared tothe industrialized countries.Personal care products are considered tobe essentials by consumers. Thus, theseproducts are somewhat insensitive tooverall economic change. Western Eu-rope with 38, North America with 25,and Asia-Pacific with 24% of the worldmarket of cosmetics and toiletries clear-ly dominate more than an 80% share of

this market, worth more than 153 billionEuro in 2003. The incombinable cametrue: In 2003, the innovation of the yearwas a facial washing gel combining ahigh cleansing efficacy with a very lowskin irritating score.In the global market for industrial clean-ing in the food and beverage industry(about 3.5 billion Euro) there are onlytwo global players – Ecolab and JohnsonDiversey Inc., the others being thousandsof small local or regional companies. In-dustrial cleaning is based on business-to-business relationships. The client de-mands integrated solutions encompass-ing chemicals, dispensing equipment,software, staff training, and support ser-

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Fig. 1 The global surfactant market by end-user application(Source: U. Lehner, Henkel).

Fig. 2 The global surfactant market by suppliers(Source: U. Lehner, Henkel).

Split in Value in 2003 of global surfactant market Market shares by value in 2003 of global surfactant market

Fig. 3 Estimated future demands will be in Asia-Pacific (Source: U. Lehner, Henkel).

Surfactants volume forecast for the household detergent sector (base 2001 = 100%)

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vices. Acting as a global player in thismarket means that the business partnershave to be global, too.The market for metal cleaning amountsto approx. 650 million Euro. Bigger andvery small suppliers share this marketamong themselves. Henkel’s share is ap-prox. 27%, followed by the direct com-petitors Chemetall and Kluthe. There is afurther demand for new high-perfor-mance surfactants, especially for suchproducts which are low-foaming underhigh pressure and at low temperatures.As D. Ferrari, Huntsman PerformanceProducts, in his Plenary Lecture »The Sur-factant Value Chain« pointed out thesurfactant industry is facing unprece-dented pressures around raw materialsprices, exacerbated by extreme volatilityin gas pricing, and has been fighting»this two-headed price and volatilitydragon for three years«. The value chainhas to change with regard to efficiency,sourcing, rationalization (consolidation),and innovation. Safety remains a funda-mental requirement in everything that isdone.

Raw Materials and Processing

In 2002, the worldwide chemical indus-try used 16.8 million metric tons or 14%of the total production of oils and fats,which was 120 million (2003: 124.3 mil-lion) metric tons (Fig. 4). More than 10million tons are processed into soap.Around 4.5 million tons are used in oleo-chemical processes. According to Cognisand Sasol data the world capacity forfatty alcohols amounts to 2.15 millionmetric tons in 2002 (Table 1). The devel-opment of the world detergents alcoholcapacity is shown in Fig. 5, the total fat-ty alcohol market by application in Fig. 6.75% are used as detergent alcohols.The development of the fatty acids glob-al capacities from 1985 to 2006 is shownin Fig. 7, the fatty acids end use in Fig. 8.Typical fatty acid derivatives in a sham-poo formulation are depicted in Fig. 9.The world surfactants capacity by ethoxy-lation and sulf(on)ation is given in Fig. 10.The world surfactants consumption issummarized in Table 2. Compared to theHenkel data cited above here a moreconservative scenario is depicted.

In Western Europe and North Americathe principal demand is supplied by foursurfactant groups – LAS, AE, FES and FAS.

A different distribution is still valid forAsia, where LAS is, mainly for price rea-sons, the dominating surfactant (Fig. 11).

Fatty alcohols million tons since

Natural 1130 1931Petrobased 900 1963Coal-based 120 2002 (Sasol)

Table 1 World capacity for fatty alcohols (Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

Fig. 4 World production of oils and fats 2002, mill. mt(Source: P. Renaud and B. Brackmann, Cognis).

Fig. 5 The development of world detergents alcohol capacity, mill. mt(Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

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As J. Vaughan, Sasol Olefins & Surfactants,pointed out, the Gas to Liquids, or GTLtechnology is being developed by a num-ber of the major international oil and gascompanies, essentially to monetize strand-ed gas. The primary products from suchplants are »clean« fuels and low-sulfurdiesel in particular.Central to the emergence of GTL tech-nology is Fischer Tropsch (FT) technolo-gy, which previously has already givenrise to a new source of fatty alcoholsfrom coal as a raw material. GTL plantswill not only produce low-sulfur dieselbut also significant quantities of paraf-fins and other feedstocks suitable forsurfactant intermediates. These new feed-stocks are a challenge to the surfactantindustry to innovatively take advantageof these opportunities. Several GTL tech-nology companies have aligned them-selves with gas resource holders and oth-er partners and have announced GTL stud-ies as well as projects. It is expected thatthe first of these GTL plants will be oper-ational by 2006 if all goes according totheir project plans.A comprehensive Shell study revealed thatGTL n-paraffins have no adverse effecton both homogeneous and heteroge-neous alkylation processes. Also, LASmade from Shell GTL paraffins is ad-equately biodegradable and its surfac-tancy and detergency performance isidentical to commercially available LAS.From Shell’s point of view, taking thecost-effectiveness of the GTL paraffinscompared to kerosin-derived paraffinsinto account, by the end of this decadeGTL technology will largely replace kero-sine extraction technology to meet thegrowth in n-paraffin demand for LAB.With all this GTL paraffin potential com-ing onto the market, it is probably worth-wile considering alternate and even moreefficient ways to activate the paraffin foruse in surfactants or direct conversion ofparaffins to the desired intermediate.In the focus of manufacturing and trans-portation safety, one of the topics of theRaw Materials and Processing SectionA: once more the safety in produc-tion and distribution of ethylene oxideand the safe design and operation ofethoxylation processes as well as theTUIS system as well-proven emergencyresponse.

Fig. 6 Total fatty alcohol capacity by application (Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

Fig. 7 Development of fatty acids global capacities 1985 to 2006 (Source: K.H. Nottinger, Cognis).

Fig. 8 Fatty acids end use 2002 (Source: K.H. Nottinger, Cognis).

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The fixed bed alkylation process for themanufacture of linear alkylbenzene forthe first time implemented in 1995 hascome from a concept to a successful re-ality. This reliable and flexible technolo-gy produces a ‘high 2-phenyl‘ type ofLAB using standard olefin feedstock withlow diolefin and aromatic content.

Wellness and Sustainability

The wellness and sustainability mega-trends will have a decisive influence onthe future and because of this on the be-havior of the consumer, stressed A. Triusin his Plenary Lecture »Wellness, Sus-tainability and a Specialty ChemicalCompany – A Contradiction in Terms?«(co-author: B. Brackmann), Cognis. Manu-facturers will have to be prepared forthe changes that will take place earlyenough so as not to miss the boat. Thisdoes not just apply to manufacturers ofconsumer goods such as food, clothingand household items. Also trivial thingssuch as washing, rinsing and cleaningagents, cosmetics and lubricants, enginesand many other things will have to beadjusted to these trends in future, in or-der to be able to maintain or expandtheir position in the market.The early strategic orientation of a chemi-cal company that calls itself a specialtychemical producer is extremely impor-tant here. Solutions that enable the cus-tomer to manufacture future-orientat-ed products that correspond with the fu-ture consumer wish in good time willhave to be found. These products alsohave to suit the megatrends wellness andsustainability, in order for everybody togain in future. The skill of the supplier,the specialty chemical manufacturer, liesin early recognition of the mood of thetimes, development of the necessary cus-tomer solutions and in making the nec-essary investments in order to be able tocontinue working profitably.

New Surfactants

At CESIO 2004 some new surfactant mole-cules were presented: selectively methylbranched C15 to C16 alcohol sulfates(Neodol® 67 AS, Shell Chemicals) that pro-

Fig. 9 Typical fatty acid derivatives in a shampoo formulation (Source: K.H. Nottinger, Cognis).

Fig. 10 World surfactant capacity by ethoxylation and sulf(on)ation 2002, mill. mt(Source: B. Brackmann, Cogis, and C.-D. Hager, Sasol).

Surfactant million tons

Soap 9.0Anionics 4.5

Linear alkylbenzene sulfonate (LAS) 2.9Branched alkylbenzene sulfonate 0.2Fatty alkyl ether sulfate (FAES) 0.8Fatty alkyl sulfate (FAS) 0.6

Nonionics 1.7Alcohol ethoxylates (AE) 1.1Nonylphenol ethoxylates (NPE) 0.6

Quats 0.5Amphoterics 0.1Others* 2.4

18.2* including lignin and petroleum sulfonate, and tall oil derivatives

Table 2 World surfactants consumption 2003 (Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

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vide increased solubility and improvedhydrophobe performance; LAS with con-trolled methyl branching in the hydropho-bic chain; alkyl polyglucoside carboxylate(1) as a new anionic surfactant (Planta-pon® LGC Sorb, Cognis); tridecanol eth-oxylates based on dimeric hexene (less gelphase problems, readily biodegradable,BASF); and cleavable ortho ester typesurfactants, an interesting alternativefor the application in industrial process-es (Akzo Nobel). Future surfactant inno-vations are dry olefin sulfonates (Balles-tra), sucrose esters (Procter & Gamble)and inulin-based surfactants for person-al care applications (Orafti Non-food).New polymeric surfactants based on in-ulin are also suitable for the stabilizationof emulsions, nanoemulsions and multi-ple emulsions (INUTEC® Surfactants, OraftiBio-based Chemicals) (2).The well-known but scarcely offered sar-conisates and glutamates obtained by N-acylation of amino acids with fatty acidchlorides were recommended as a class ofversatile surfactants with key advantagesin such fields of application as dental careproducts, shaving products, shampoos, al-kaline cleaners, carpet shampoos, dish-washer detergents, and metal workingfluids (Schill & Seilacher).

Structures and Properties

The Structures and Properties Section Bcomprised new surfactant structuresalready cited above, new methods ofsurfactant characterization such as time-resolved fluorescence quenching andcryo-transmission electron microscopy,surfactant characterization outside theHLB system, exploiting synergies in sur-factant mixtures and modeling of indus-trially relevant surfactant formulations,phase behavior and rheology includingrheological properties of viscoelasticsurfactant solutions, the influence ofguest components in rheology and shearinduced structures in surfactant lamellarphases, micellar and rheological proper-ties of some highly viscoelastic zwitter-ionic surfactants and the high-through-put microemulsion phase diagram gener-ation.Other topics were the dynamics of near-zero energy emulsification, the industri-

al application of the dynamic surfacetension, the relation between macro-scopic foams and single foam films, andsurfactant-templated nanomaterial syn-thesis.

Emulsifiers and Emulsification,Dynamic Surfactants, and SurfaceModification by Surfactants

The field of emulsifiers and emulsifica-tion was one of the key issues of the In-

dustrial Applications Section C as well asthe dynamic properties of surfactantsand the surface modification by surfac-tants. Beside a review on the state of theart of emulsion technology analyticalcentrifugation for rapid emulsifier selec-tion and evaluation of emulsion stabili-ty was demonstrated.Surfactants find wide application in themanufacturing process of leather. Wash-ing, cleaning, rewetting, dispersing, de-greasing and emulsifying are the differ-ent activities of surfactants used in the

KRÜSS at CESIO 2004

With the first truly hand held bubble pressure tensiometer PocketDyne KRÜSSshowed a real alternative to the existing laboratory instruments. The well-knownbubble pressure tensiometer BP2 now determines diffusion and adsorption con-stants of surfactants in addition to dynamic surface tension values. The fully mod-ular contact angle measuring system DSA100 determines surface free energy ofsolids, surface and interfacial tension of liquids as well as interfacial rheologicalproperties by a unique combination of oscillating/expanding drop module. In caseone needs to find out the right concentration range for determining the CMC val-ue, the right choice is the Processor Tensiometer K100 series. It can be used to de-termine the CMC value automatically without having an idea of the concentra-tion range. Thanks to two dosing units the volume of liquid added is aspiratedagain immediately after mixing. This way the whole liquid volume is kept con-stant. In case of a high throughput application KRÜSS offers the Delta 8 ten-siometer. It can measure the CMC value for 8 different substances in parallel inabout 2 minutes. In a cooperation with company AlCove, KRÜSS GmbH offers tosolve customer requests by molecular modeling.

Fig. 11 Major surfactant markets by region (Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

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individual steps of leather making. It couldbe shown that new surfactants based ona C10 alcohol are an ecologically and eco-nomically viable replacement for APEOs.Carbon dioxide has potential as a substi-tute for the currently most utilized dry-cleaning solvent, perchloroethylene. Thelimited solvency of CO2 for polar mole-cules can be overcome by the addition ofmiscible surfactants such as alcohols,polysiloxanes and alcohol ethoxylates.Most of the water-based knowledge onnonionics can be transferred to the CO2-based systems using the newly devel-oped HCB concept – the hydrophilic CO2-philic balance.Multivariate data analysis enables theprediction of adjuvant performance fromthe surfactant properties.Industrial processes are becoming fasterand faster. Fast diffusion of amphiphilesto interfaces and the formation of inter-facial films to lower the interfacial ener-gy are the fundamental molecular mech-anisms which have to be optimized forall high-speed spraying and wettingprocesses. Processes in which ‘new‘ inter-face is generated in fractions of a secondare significantly influenced by the dy-namic behavior of the surfactants in-volved. Thus, the dynamic properties ofsurfactants play a more and more im-portant role for a profound understand-ing of their industrial application. An im-portant example is the flotation de-ink-ing in the recycling of waste paper.A higher level of process quality controlcan be achieved by the in-line analysis ofsurfactant properties. This was shown ina metal cleaning process.Surfactant molecules have long beenused for surface modification in order toinvoke hydrophobic surfaces, e.g. inflotation, or hydrophilic surfaces, such asin the stabilization of dispersions. In thiscontext, surfactants play an importantrole in the textile industry, especially inthe production and processing of fibers.Polyampholytes are shown to be suitablefor the surface modification of fiber-re-inforced plastics.Polymeric dispersants or surface-activepolymers can be prepared by graftinghydrophobic chains to a hydrophilicbackbone, grafting hydrophilic chains toa hydrophobic backbone, and alternat-ing hydrophilic and hydrophobic seg-

ments in the chain. Phenomenologicalresults in their application were corre-lated to fundamental parameters such ascontact angle, interfacial tension andwork of cohesion.Coating additives normally do not trig-ger new developments in coatings butthey can be the crucial factor in makinga new and innovative coating systemsuccessful in the market.Other examples for surface modifica-tions are glass fiber sizing and the anti-corrosion properties of gemini surfac-tants in the α,ω-alkanediyl dimethylalkyl ammonium bromide series.

Nanostructured Surfaces – New Cleaners Wanted

In his Plenary Lecture »New SurfactantStructures: The Key for Chemical Nano-technology and New Processes« M. An-tonietti, Max Planck Institute of Colloidsand Interfaces, Golm, Germany, statedthat »with its key role in chemical tech-nology and biology, we regard the han-

dling of surfaces with appropriate mole-cules for all purposes as key ‘know-how‘for the next generation of colloid chem-ical experiments and products«. It wasshown that ‘new‘ surfactant structurescarry the promise to expand the perfor-mance profile of nowaday surfactants tohandle also more critical surface stabi-lization problems, e.g. the efficient sta-bilization of very large surfaces or theclosure of the ‘cohesion energy gap‘ bymultipolarity and adaptive construction.»It is with good reason foreseeable«, An-tonietti concluded, »that such surfac-tants will allow to shape new ‘world scale‘applications, such as nutrition, buildingmaterials, nanocomposites, insulatingnanofoams, or in the redesign of phar-maceutical actives. Chemical nanotech-nology is deep down based on the han-dling of interfaces, and surfactant sciencewill have its significant share«.One of the first products the customercame into contact with nanotechnologywere easy-to-clean-coatings on glassand sanitary ware. In the last years, mostcompanies offered these easy-to-clean-

L.U.M. GmbH at CESIO 2004

L.U.M. GmbH Berlin – Specialist for rapid and efficient characterization of con-centrated dispersions and manufacturer of analytical instruments for dispersionsanalysis draw a favorable balance of their participation in the CESIO conferenceand exhibition.At the exhibition L.U.M. GmbH presented its newest generation of dispersionanalysers – the ’Complete Dispersion Laboratory’ – LUMiSizer. This new device en-ables the characterization of stability of dispersions (emulsions, suspensions), theirparticle size as well as the evaluation of the efficiency of dispersants, emulsifiers,flocculants and demulsifiers by multisample analytical centrifugation (12 sam-ples simultaneously). L.U.M. GmbH used the opportunity to contact potential new customers and dis-cuss with specialists from all over the world new methods and options to solvetheir current problems.During the conference program L.U.M. presented a paper entitled »Rapid emulsi-fier selection and evaluation of emulsion stability by analytical centrifugation« inthe Industrial Applications Section. A poster demonstrated the efficiency of mul-tisample analytical centrifugation for selection of additives, their optimum con-centration and composition with examples of carbon black dispersions, lime dis-persions and emulsification.

(1) www.lum-gmbh.com(2) www.AppliedColloidsSurfactants.info/1_1.html(3) T. Sobisch, D. Lerche, 2004 http://preprint.chemweb.com/chemeng/0405001

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coatings only on demand, but since 2003some companies have started to deliverfirst series with functional coatings. Thesenanotechnology-enhanced products havebegun to revolutionize the cleaning be-havior of people. Self-arranging coatingsconsisting of modified nano-silica stickextremely well on glass and ceramics butoffer at the same time an almost 100%anti-stick surface against water, grease orsoil.The consequence of this trend is that theparadigms in the detergent industry mustshift, because new surfaces which needto be cleaned and taken care of alsomean new requirements for the cleaners,new problems and new products. The pri-orities of the cleaner of the future couldrather be to preserve and to support thecoated surface than »simply« to removesoil. Today, in many cases the cleanercompositions are not suitable for clean-ing coated surfaces, because they eitherdo not wet the surface properly, are me-chanically and chemically too aggressiveor lead to residues which affect thefunction of the coating.In the sanitary and glass ware businessthe hydrophilic and the hydrophobic ap-proach for easy-to-clean surfaces com-pete with each other. It does not matterwhich coating principle will finally makeit in the market. The key point is thatnanotechnology begins to change thecustomer’s desire for an intelligent clean-er into a desire for an intelligent surface.A very interesting field in the future willbe the combination of detergents andnanostructures. Nanogate is currentlydeveloping cleaner compositions, whichduring cleaning render the cleaned sur-face either water-repellent or hydrophilic.Moreover, these cleaners can also beused to coat originally uncoated surfaceswith a semi-permanent hydrophilic orhydrophobic easy-to-clean effect whichlasts for some months.Molecular modeling simulations wereused as a novel technique to character-ize nanostructures. Surface-modified alu-minas serve as organic nanodispersions.

From Closed Loop Cleaning toWellness Activities

In the Household, I&I and Personal CareSection D a broad spectrum of topics was

presented. One of them was the increas-ing legislative, customer and consumerpressure on the formulator of RetailerBrand Cleaning Products. From this sideit is perceived that the strength anddepth of these constraints are not fullyunderstood by base raw material manu-facturers. This increasingly difficult en-vironment makes it a necessity thatmanufacturers and formulators find bet-

ter ways of working together.A closed loop cleaning process with bothwater and chemical (detergent) reusewas presented. A preliminary analysis ofthe different formulations used indicat-ed that an all-nonionic formulation maybe best suited to this recycling process.For the sustainable central processing ofhome laundry which is of great interestalso in developing countries with large

Two Weaknesses of Traditional Surfactants in the Context ofNano-Operations

»Wrong« polarity design: Most surfactants show something which is called the»cohesion energy gap«, that is they are composed of a very polar and a quiteunpolar moiety only. This implies that many surfaces and molecules cannot beappropriately addressed, as they find no counterpart in the molecular struc-tures. In addition, self-adjustment to the surface is impossible due to molecularlayout.»Wrong« geometry design: For »Nano«, a layer thickness of 3 nm to be effectiveis an incredible waste of material. Model experiments with target structures in-dicate that the same job can be done with 0.3 nm thickness, that is a tenth ofsurfactant load.Possible solutions: Biomimetic approach with flat stiff structures (cholic acidsystems, saponines, deferoxamines, or didepsides), or short polymeric structuresas stabilizers (proteins, oligosaccharides), double hydrophilic copolymers, hy-drophilic-«biophilic« stabilization or »chimera« polymers.

(According to M. Antonietti)

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urban population centers a microfiltra-tion process was proposed. This step iskey to effectively removing contami-nants from the water while allowingsome reuse of detergent ingredients.Although methyl ester sulfonates (MES)have been manufactured since 1991 thissurfactant has not gained widespreaduse because of some technical issuesarising in MES application to laundrypowder detergent. Recently, a novel sul-fonation process for C16/C18 methyl estersulfonate from palm oils and some typesof easy-to-handle delivery forms weredeveloped.With the emergence of hydrophobebranching one should pay attention tothe surfactant performance as a func-tion of this branching. In this context de-tergent alcohols ranging from 99% lin-ear to 99% branched have been evalu-ated. Hydrophobe branching dramati-cally affects foaming, leading to reducedperformance in dishwashing as branch-ing increases. A similar effect has beenobserved in liquid hand-soap formula-tions. Fabric detergency is improved byincreasing branching, since the branchedsurfactants are more soluble than the es-sentially linear homologs.Textiles play an important role in pro-viding us with holistic feeling of well-be-ing. They protect us like a ‘second skin‘from harmful external influences likesunshine and rain, they regulate ourtemperature and moisture balance, andthey decorate our body, thus impartingadditional beauty and attractiveness andpampering us with tactile stimuli. Thesenses which are most activated whenperceiving textiles are of course visionand tactile feel. As a consequence, a tai-lor-made sensory assesment has beendeveloped for spray and softener appli-cations, which is focused on optical andhaptic parameters. Furthermore, for ob-jectively measuring emotional states ofmind via psycho-physiological parame-ters the so-called Objective EmotionalAssessment (OEA) has been developed.Beside key benefits derived from siliconessuch as thread lubrication and fabricsoftening, more recently, there are at-tempts to translate more of the knowntextile industry technology into con-sumer laundry benefits. Examples are im-provements in fabric dewatering, fabric

elasticity, shape retention and perfumerelease. The exploitation of these tech-nologies is applicable primarily in fabricconditioners but development of innov-ative and cost effective solutions forpowder and liquid detergent applicationsis a logical and important extension.Zinc ricinoleate is a powerful means forcomplexing nucleophilic malodor mole-cules. The results of molecular modelinghave led to the development of a zinc ri-cinoleate-arginine blend with addedbenefits such as water solubility and lowstain risk.A classification of the Industrial andInstitutional (I&I) market by businesssector and application area is given inTable 3. On a global scale, one can iden-tify the following trends:

• An increased need for greater pro-ductivity and operational efficiency.

• The requirement for greater produc-tivity demands fool-proof, extremelysimple and low- or no-maintenancecleaning and sanitation systems.

• Migration towards global accountmanagement.

• In the area of food services, centralkitchens are rapidly proliferating as

companies attempt to benefit fromthe synergies of centralized opera-tions.

• Increased awareness towards foodsafety, emerging diseases and bio-ter-rorism.

• An aging population requiring safehealth care and an increase in thenumber of long-term care facilities.

The challenges facing the I&I industry re-quire an intimate collaboration betweenthe I&I customer, the I&I companies andthe chemical industry.A new approach to formulate cleaningproducts with microemulsions was pre-sented as well as tests for optimizingproducts and formulations with low-foaming surfactants as rinse aids.

Personal Care

The CESIO papers in the field of person-al care covered expectations and inno-vations in surfactants for personal prod-ucts, the application of new surfactantscited above, dermatological and toxico-logical aspects as well as applicationtechnologies in, for instance, skin care.

Table 3 Classification of the Industrial and Institutional (I&I) market by businesssector and application (Source: G. Clark, Johnson Diversey).

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The addition of the mild co-surfactantsodium cocoyl glutamate (SCG) to sodi-um laureth sulfate (SLES) containing dai-ly shower products resulted in a signifi-cant reduction of SLES adsorption on hu-man skin which improves skin care. SCGitself adsorbed only in neglible amountson the skin from SLES/SCG mixtures.Multifunctional building blocks haveproven in gemini surfactant applicationfor personal care and beyond. Sodiumdicocoylethylenediamine PEG-15 sulfateis Sasol’s example of a well-balancedgemini surfactant as key component inhighly flexible building blocks – anemulsifier/dispersant (CLH) with behenylalcohol, and glyceryl stearate citrate,

and an cleansing/dispersant buildingblock (CLF) with sodium lauroyl lactylate.The next innovation step can be summa-rized under the heading ‘easy processing‘(room temperature, no homogenization)– an emulsion concentrate that can befilled with any oil and becomes self-emulsifying. The latest version is an evenmore flexible concentrate which allowsthe use of any oil and forms highly sta-ble nano-emulsions.Since the paradigma of absolutely linearfatty alcohols and their derivatives forcosmetic application has been overcomeit could be shown that carefully select-ed oxo alcohols and their derivatives aresuitable also in this area.

Structured surfactant formulations (SSF)have been utilized for almost twentyyears in many different products, appli-cations and markets. The main feature ofthese systems has been their ability tosuspend insoluble, functional particu-lates, thus preventing their sedimenta-tion in mobile liquid formulations. Tradi-tional SSF systems comprise surfactantsthat form close-packed lamellar orspherulitic structures in the presence ofelectrolytes. Recent advances includenon-aqueous structured systems capa-ble of suspending water-sensitive mate-rials such as peroxygen bleach and acti-vators, electrolyte-free structured sys-tems for potential pharmaceutical appli-

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cations, and sugar-structured surfactantsystems which form clear gels with ex-cellent suspending properties and en-hanced visual effects.The design of new surfactant packagesfor skin care products enables the im-provement of enhanced water resistanceof sunscreen formulations, segregationof active ingredients in multiple emul-sions, less irritating cleansing productsand lighter feeling oil continuous creamsand lotions.Numerous thickeners are available tocosmetic formulators in order to en-hance the viscosity of foaming cosmeticproducts going from classical hydrocol-loids to polymeric high molecular weight(MW) surfactants and low MW nonion-ics or diethanolamine free alkanolamides.Although there are so many raw materi-als to choose from, the direct replace-ment of the well-proven Cocamide DEAremains a difficult task. In a comparativestudy the superiority of an alternativefrom point of view of workability andviscosity build-up performance in a for-mulation could be shown: an easy-to-handle liquid product based on CocamideMIPA and Laureth-4 that gives a similarviscosity profile as Cocamide DEA at alltested conditions.

Environment, Toxicology,Regulatory Affairs

In the focus of the Section E (Environ-ment, Toxicology and Regulatory Affairs)were Product Stewardship, the newChemicals Policy (REACH), Risk Assess-ment of Surfactants, the new EU Deter-gents Regulation, and EnvironmentalProperties of Surfactants.Coordinated measures of industry andauthorities have proven as a successfulalternative to administrative regulations.The instrument of regulation is essentialfor basic demands such as the biodegrad-ability of surfactants. Agreements gen-erally allow a faster implementation, areeasier to modify and enable the involve-ment of stakeholders according to theirimportance for the area to be ruled. Be-side regulations and agreements theGerman Cosmetic, Toiletry, Perfumeryand Detergent Association (IKW) resort-ed to the instrument of recommendations

to lay down rules on environment-relat-ed advertisements. A recommendation of-fers an adequate scope for estabishing acode of conduct, which is factually well-founded and ethically postulated.As a case study of the evaluating surfac-tants based on their impact on the envi-ronment the so-called Greenlist processof SC Johnson & Son was analyzed. Thisprocess has stimulated innovation withmore sustainable product design by pro-viding information, training and motiva-tion. The EC sponsored OMNIITOX (Oper-ational Models and Information Tools forIndustrial Application of Ecotoxicologi-cal Impact Assessments) detergent casestudy revealed that different LCIA (LifeCycle Impact Assessment) methods re-sult in different product rankings re-garding potential impacts on aquaticecotoxicity. Therefore, the challenge forOMNIITOX is to develop an agreed method,which overcomes the situation of di-verging results.The Japan Surfactant Industry Associa-tion (JSIA) has just started a new pro-gram named SRA (Surfactant Initial RiskAssessment) plan to arrange the alreadygained information for the full range ofsurfactants. JSIA considers the exchangeof experiences worldwide very impor-tant for sustainable development.It is well-known that in October 2003 theEuropean Commission adopted a propos-al for a European Parliament and Coun-cil regulation on the Registration, Eval-uation, Authorisation and Restrictionsof Chemicals (REACH). According to thisproposal the industry would be obligedto register all marketed chemicals above1 ton annually within 11 years followingthe entering into force of the new regu-lation. A minimum data set would be re-quired for chemicals between 1 and 10tons and additional information – the ex-tent depending on the tonnage – wouldhave to be provided for chemicals ex-ceeding 10, 100 and 1000 tons. Above 10tons, industry would have to draw up aChemical Safety Report which includes arisk assessment. The results of this as-sessment would have to forward to thedown stream users transformed in thetraditional Data Safety Sheet in order toenable them to meet their responsibili-ties. If implemented in its current formREACH will have a highly negative eco-

nomic impact on the entire economyin the EU. This was stressed in PlenaryLectures as well as in contributions ofVCI officials. In particular, supply chainswhich rely on specialized products – suchas surfactants for specific applications –will be affected.From the VCI’s point of view the follow-ing steps are necessary in the legislativeprocedure to achieve a balanced andworkable regulation:

• Impacts of the proposed provisions –in particular on the competitivenessof the European industry, on ecom-nomic growth, employment and in-novation – must be examined thor-oughly by a neutral party before theproposal for a Regulation goes intothe final phase of the legislative pro-cedure.

• The workability of the REACH systemand efficiency of its procedures mustbe fully examined and tried out bycompanies and public authorities.This should be done in Europe-widepilot projects jointly with the Com-mission, competent national authori-ties and the concerned companies.

As to ‘comprehensive risk assessments‘and ‘targeted risk assessments‘ the datarequirements may differ – another dri-ver to foster international cooperation.A good example for international safetyassessments is the LAS product chain(Table 4).A key conclusion from this activity is thatthere is an extensive database of infor-mation on these materials, and overallthe data – and 35 years of safe use –demonstrate low concern (little risk) forpotential health or environmental ef-fects.Although no risks associated with the useof LAS have been found, LAS is still dis-criminated by criteria for ecolabelling.Furthermore, the causative agent formuch environmental damage has beenoften rashly and erroneously attributedto surfactants and their degradationmetabolites present in the aquatic envi-ronment, sludge, sediment or seawater.In spite of the fact that the industry hascarried out a lot of research work and riskassessments addressing the various envi-

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ronmental compartments, surfactantshave remained the subject of attentiondue to a combination of their inherentenvironmental properties, their strongpresence in consumer products and theirlarge production volume.Bioconcentration factors increase withincreasing hydrophobicity. Consideringthe hydrophobicity dependence of theuptake rate constants as well as the sur-factants propensity to biotransforma-tion is a viable (and currently explored)option for providing a realistic estimateof the bioconcentration potential of sur-factants in the environment.The risk assessment activities related toamine oxides are a good example for thegrowing international cooperation be-tween the US, Japan, and Europe in thisfield. Another example for working with-in a consortium and extensively exchang-ing information within value chain is thedevelopment of risk assessments forthe family of alcohol-based surfactants(ERASM/HERA/HPV initiatives).The new EU Detergents Regulation mod-ernizes the EU legislation in two impor-tant respects. First, it replaces the earli-er tests for primary biodegradability withtests for ultimate biodegradability andextends the scope of the legislation to alltypes of surfactant. Second, it introduceslabelling requirements for detergents forthe protection of human health and ofthe environment. A number of open is-sues have been identified in the Regula-tion with deadlines for their resolution.One of these issues is the anaerobicbiodegradability of surfactants. A studyon this subject has been carried out forthe Commission by the Fraunhofer Insti-tute for Environmental, Safety and En-ergy Technology UMSICHT. A decision onwhether to proceed to a legislative pro-posal will be made following evaluationof the report by the appropriate Com-mission Scientific Committee. Any suchlegislative proposal must be made with-in five years of the date of publication ofthe Regulation.An ERASM (AISE-CESIO) Expert Panelconcluded in 1999 that anaerobicbiodegradabilty does not have the sameenvironmental relevance as aerobicbiodegradability and »should not be usedas a pass/fail property for the environ-mental acceptability of surfactants

which are readily biodegradable underaerobic conditions«. Key findings sincethe ERASM report confirm this conclu-sion.Data from the literature are not appro-priate to predict the ultimate biodegrad-ability of surfactants today. Particularlyin the case of polymeric surfactants sev-eral parameters – many more than in thepast – may be varied and adapted to fi-nally combine high performance withultimate biodegradability.EO/PO block copolymers are known tofail primary biodegradation requirementsand also ready biodegradation tests ofthe OECD 301 series. Therefore, they haveincreasingly replaced in detergent for-mulations. New data surprisingly showsthat polypropylene glycols (PPGs) withmolecular weights up to 2500 do fulfillthe criteria for ready biodegradability.As a result, a number of EO/PO blockcopolymers with varying compositionsand molecular weights have been re-tested and, like the PPGs, passed the cri-teria. There is no proven explanation forthis phenomenon. Actual theories focuson adaptation of the microorganisms thathas been facilitated by an increasing ex-posure to structurally related chemicalcompounds in the aquatic environmentover a prolonged period of time.Metabolic studies enable ready biodegrad-ability classification of classes of fattyamine derivatives characterized by hy-drophilic moiety. Ecotoxicity studies onthe nematode, C. elegans, have shownthat the cationic exchange capacity ofsediments reduces cationic surfactant

toxicity. Field studies on the adsorption/desorption of LAS in agricultural soils re-vealed that LAS leaching was limited on-ly to the first few cm layer of the soil.

7th World Surfactants Congress

For the second time, the next World Sur-factants Congress will take place in Parisfrom June 21 to 25, 2008.

References

(1) H.G. Hauthal, A New Anionic Surfactant – AlkylPolyglucoside Carboxylate, SÖFW Journal 2004,English version, 130 (9), 86, 88);

(2) K. Booten, B. Levecke, Polymeric, carbohydrate-based surfactants and their use in personal careapplications, SÖFW Journal 2004, English ver-sion, 130 (8), 10-16

*Author’s address:Prof. Dr. Hermann G. Hauthal

Rosenstrasse 2006237 Leuna

GermanyEmail: HGHauthal@t-online.de

Institution or Initiative Products included

International Council of Chemical Associations benzene, linear High Production Volume (HPV) assessment and the alkylbenzene (LAB),OECD Screening Information Data Set (SIDS) programs LAB alkylate bottoms,

LAS, paraffins

US Environmental Protection Agency (EPA) LAB sulfonic acids,HPV assessment program LAS-related materials

AISE-CESIO Health and Environmental Risk LASAssessment (HERA) of detergent ingredients in Europe

Table 4 International safety assessments of the LAS product chain.