W III. Formulation Scan! W II W I. What is Solubilization?! All phase diagrams contain a. Phase behavior!

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1 / 235 44 th American Chemical Society National Meeting, New rleans LA USA, April 6-10, 2008 2 / 44 What is Solubilization?

Rojas water polyphasic zone oil height of polyphasic zone generally at center 3 / 44 W All phase diagrams contain a monophasic zone S S 1 1 W 1 3 If a formulation variable is changed (along a

1 1 / th American Chemical Society National Meeting, New rleans LA USA, April 6-10, / 44 What is Solubilization? it is the ability of a surfactant to produce a monophasic system containing both oil and water surfactant (+ alcohol) S+A monophasic zone Jean-Louis Salager, Ana Forgiarini, Cesar Scorzza and rlando Rojas water polyphasic zone oil height of polyphasic zone generally at center 3 / 44 W All phase diagrams contain a monophasic zone S S 1 1 W 1 3 If a formulation variable is changed (along a Formulation scan) How does solubilization change? W S Bourrel M., Schechter R. S., Microemulsions and Related Systems, Marcel Dekker, New York / 44 W I Formulation Scan W III Salinity ptimum Formulation Phase behavior W II 5 / 44 The height of polyphasic zone at fixed oil/ water composition (e.g. 50/50) is monitored 6 / 44 Phase A a bicontinuous microemulsion is S Phase B is a bicontinuous microemulsion A B Height S + A Formulation Scan lowest height = maximum solubilization at optimum formulation Bourrel M., et al., The Topology of phase boundaries for oil-brinesurfactant systems and its relationship to oil Recovery, Society of Petroleum Engineers J., 22 (1), (1981) swollen micelle S1 micelle φ bicontinuous microemulsion 1φ A B 3φ φ swollen micelle S2 micelle W Salager J. L., Antón R. E. Ionic Microemulsions. In Handbook of Microemulsions Science and Technology, Kumar P., Mittal K., Eds. Chapter 8, Dekker. New York

7 / 44 Bicontinuous Structures with zero curvature 8 / 44 Bicontinuous Structure with zero mean curvature Random bicontinuous structure Schwartz surface Scriven S.

Solubilization at crossing 10 / 44 Tension-Solubilization Relationship Solubilization varies as the inverse of interfacial tension many applications of optimum formulation Enhanced oil recovery Crude

2 7 / 44 Bicontinuous Structures with zero curvature 8 / 44 Bicontinuous Structure with zero mean curvature Random bicontinuous structure Schwartz surface Scriven S., Nature 263: 123 (1976) Characteristics of microemulsion and of oil-water interface in a Winsor III diagram 9 / 44 Solubilization Parameters SP water in m SP oil in m 3 φ Formulation Scan Maximum Solubilization at crossing 10 / 44 Tension-Solubilization Relationship Solubilization varies as the inverse of interfacial tension many applications of optimum formulation Enhanced oil recovery Crude oil dehydration Emulsion breaking Detergency Remediation Solubilization in microemulsion... INTERFACIAL TENSIN (mn/m) ptimum Formulation Vo/Vs mo mw l m u 3 φ Salinity, % NaCl SP* Vw/Vs Formulation SLUBILIZATIN PARAMETERS ml/ml 11 / 44 oil () water (W) Winsor s Ratio (1954) between molecular interaction energies surfactant (C) Aco Acw R < 1, R = 1 or R > 1 related to phase behavior R = Aco Acw R = 1 at optimum formulation Winsor P., Solvent Properties of Amphiphilic Compounds, Butterworth London (1954) 12 / 44 Winsor s R Maximum Solubilization when N = D R = Aco = N = 1 Acw D but... various cases R = 1 = = = Is it the same thing? No 2

3 13 / 44 According to Winsor s premise Solubilization increases when interactions increase on both sides of interface But there is a limit 14 / 44 In some cases Winsor s premise does not explain the observed increase in solubilization Lipophilic Additive increases solubilization 20 SP* ml/g M Surfactant Ethoxylated ctylphenol (EN near 5) Isooctane, WR =1, 25ºC when chain reaches carbon atoms, the surfactant precipitates (Krafft Temperature) 10 Additive P 0 E P 1 E % aditivo en aceite P 1.5 E 0 % Additive in oil P 3 E GRACIAA A., et al. Improving Solubilization in Microemulsions with Additives - 1 : The lipophilic linker role, Langmuir 9 : (1993) 15 / / 44 Proposed Mechanism The Lipophilic Linker increases interactions on the oil side by ordering the molecules deeper inside the oil bulk phase IL IL Graciaa A. et al. Improving Solubilization in Microemulsions with Additives - Part I : The lipophilic linker role, Langmuir 9, 669 (1993) Graciaa A. et al., Improving Solubilization in Microemulsions with Additives - Part II : Long chain Alcohol as Lipophilic Linkers, Langmuir 9, 3371 (1993) Salager J. L. et al. Improving Solubilization in Microemulsions with Additives. Part III: ptimization of the Lipophilic Linker, J. Surfactants & Detergents 1, 403 (1998) ordered zone WATER ordered zone Interface INTERFACE WATER Lipophilic Linker 17 / 44 The Lipophilic Linker 18 / 44 Examples of Lipophilic Linkers does not adsorb at interface (it is not a cosurfactant) is a slightly polar oil (or a very lipophilic amphiphile) is located inside oil phase near interface (interfacial segregation) gets oriented perpendicular to interface stretches the reach of surfactant in oil (without producing precipitation) Long chain n-alcohols ( > 8) Long chain alkylphenols ( > 8) idem slightly ethoxylated (EN < 2) Single chain esters (ethyl oleate) probably other linear lipophilic amphiphiles Graciaa A., et al., Improving Solubilization in Microemulsions with Additives - Part II : Long chain Alcohol as Lipophilic Linkers, Langmuir 9 : (1993) 3

4 19 / 44 Lipophilic Linker Role The L.L. stretches (in situ)... the surfactant hydrophobic tail 20 / 44 Hydrophilic Linker Same role on the water side di-hexyl-sulfosuccinate The L.L. produces a slightly polar zone inside the oil phase, near the interface The H.L. produces a slightly less polar zone in the water phase, close to interface Uchiyama H. et al. Supersolubilization in Chlorinated Hydrocarbon Microemulsions. Solubilization Enhanced by Lipophilic and Hydrophilic Linkers, Industrial & Engineering Chemistry Research 39 : 2704 (2000) Acosta E. et al, The Role of Hydrophilic Linkers, J. Surfactants Detergents, 5: 151 (2002) 21 / 44 Naphtalene Sulfonate = hydrotrope S 3 Na H 3 C H 3 C H 3 C Hydrophilic Linker S 3 Na S 3 Na Di-butyl Naphtalene Sulfonate = hydrophilic surfactant H 3 C-CH 2 -CH 2 -CH 2 H 3 C-CH 2 -CH 2 -CH 2 S 3 Na Mono/Dimethyl Naphtalene Sulfonate = hydrophilic linker 22 / 44 Lipophilic and Hydrophilic Linkers Combining LL and HL increases solubilization performance in many systems : Hydrocarbons, mono, di and triesters, natural oils, tri and tetrachloroethylene (denser-than-water oils), motor oil, terpenes, squalane etc For various applications: Detergency, hard surface cleaning, remediation processes, drilling fluids, completion, spacer and workover fluids, etc Acosta E., et al., Environmental Science Technology 36: (2002) Acosta E., et al., J. Surfactants Detergents, 6: (2003) 23 / 44 Lipophilic and Hydrophilic Linkers 24 / 44 Go-thru amphiphilic Linker oil Lipohilic Linker adsorbed Surfactant Hydrophilic Linker water produce: Better match (oil does not contact water) Continuous polarity variation It extends interactions on both sides of interface (low MW diblock polymer) At low concentration there is no solubility problem Considerable Enhancement of Solubilization LL effect anchored at interface HL effect Jakobs B. et al., Amphiphilic block copolymers as efficiency boosters for microemulsions, Langmuir 15, 6707 (1999) 4

25 / 44 26 / 44 Favorables factors are : continuity in interfacial transition and a good match on both sides 27 / 44.

5 25 / / 44 Favorables factors are : continuity in interfacial transition and a good match on both sides 27 / the same effect could be attained with a single molecule : extended surfactant Surfactant + Lipophilic Linker? hydrophobic chain hydrophilic group Extended Surfactant Spacer arm is hydrophobic but slightly polar PLY- PRPYLENE XIDE 28 / 44 Extended Surfactants (1 rst Generation) dodecyl poly-propylene oxide (variable length) ethoxy (2E) sulfate sodium salt Miñana-Perez M. et al., Solubilization of Polar oils in Microemulsion Systems, Progress Colloid Polymer Science, 98 : (1995) 29 / 44 Extended Surfactant Properties depend on When PN increases CMC decreases Cloud Point is lowered Propylene xide Number (PN) ptimum Salinity (3φ) decreases Conclusion: When PN increases surfactant becomes more lipophilic PP chain is part of the "tail" 30 / 44 Extended Surfactant Properties produce a HIGH SLUBILIZATIN and LW TENSIN particularly with natural oils Soya oil = natural triglyceride SP (ml/g) WR = 1 T = 35 C 1.25 wt.% extended Surfactants Ethyl leate Miñana-Perez M. et al., Colloids and Surfaces A. 100 : (1995). Hexadecane Mygyol 812 Soya oil PRPYLENE XIDE NUMBER 5

31 / 44 Micelar agregation of extended surfactant 32 / 44 Micelar agregation of extended surfactant Intermediate polarity zone Lipophilic Core Hydrophilic Groups computer simulation courtesy Alvaro

6 31 / 44 Micelar agregation of extended surfactant 32 / 44 Micelar agregation of extended surfactant Intermediate polarity zone Lipophilic Core Hydrophilic Groups computer simulation courtesy Alvaro Fernández computer simulation courtesy Alvaro Fernández 33 / 44 Potential Applications Single phase water-oil mixtures bladder stone dissolution single phase dressing vegetable oil extraction environmental remediation petroleum well cleaning Microemulsions for injection in blood stream (most pharmaceutical products are oil soluble) Soak-only Detergent Formulation (no stirring required) 34 / 44 ptimize nature and size of the 3 pieces: Adjust structure to oil nature New generation of extended surfactants: Biocompatible (e.g. sugar) polar group Determine mxing rules Conventional + extended surfactants 35 / 44 2 nd Generation of extended surfactants for biocompatible applications nice polar group taylored spacer arm Fatty acid derivative (hydrophobic tail) Physico-chemical Properties of theses Products are under study 36 / 44 Recent Publications Scorzza C. et al., Synthèse de dérivés polypropilèneglycol à tête glucidyl ou ityl comme surfactifs, XVIIº Journées Chimie des Glucides, Tregastel, France, June 1998 Scorzza C. et al., New amphiphilic polypropileneglycol derivatives with carbohydrate polar head, 24º Congr. An. Comite Español Detergencia, Barcelona, Spain, May 1999 Goethals G. et al., Spacer arm influence on glucido-amphiphilic compound properties, III International Meeting of the Portuguese Carbohydrate Chemistry Group and I Iberian Carbohydrate Meeting, Aveiro, Portugal, Sept , 1999 Goethals G. et al., Carbohydrate Polymers, 45: (2001) Salager et al., Enhancing Solubilization in Microemulsions. From Classic trends to Novel Extended Surfactant Structures, Pubs 14th International Symposium Surfactants in Solution, Barcelona, Spain, June 9-14, 2002 Scorzza C. et al., J. Surfactants Sabatini & Detergents 5: (2002) Scorzza C. et al., J. Surfactants & Detergents 5: (2002) Fernandez A. et al., J. Surfactants & Detergents 8: (2005) Fernandez A. et al., J. Surfactants & Detergents 8: (2005) Salager J. L. et al. Enhancing Solubilization in Microemulsion State of the Art, J. Surfactants Detergents 8: 3-21 (2005). 2 publications waiting. Goethals G. et al., Spacer Arm influence on Glucido-amphiphilic Compound Properties, Carbohydrate Polymers, 45 : (2001) 6

7 37 / 44 Semicommercially available compounds 38 / 44 Polar heads (simple or combined) currently synthesized and tested in Lab. FIRP Sasol (Condavista) Seppic Hunstman Linear C12-C18 chain attached at end or center saturated or unsaturated Spacer to be tested Poly C2/C3/C4 Cellulose compounds Gradual polarity change sulfate ethoxy-sulfate carboxylate ethoxy-carboxylate C6 sugars xylitol (C5 sugar) di-xylitol ethoxy-xylitol carboxylate & xylitol carboxylate & glucose thers 39 / 44 extended soaps 40 / 44 Hydrophilic Linker Lipophilic tail Lipophili c linker spacer Hydrophilic head R= alkyl tail R-(--PP) n --Et--Et Lipophilic Linker H H H Hydrophilic linker Facilitates synthesis extended glycoside Sugar polar group H 41 / / 44 R = dodecyl = Xylitol extended di-xylitol Increase in water solubility and HLB 7

43 / 44 44 / 44 Current best solubilization : 1 gram of high performance extended

8 43 / / 44 Current best solubilization : 1 gram of high performance extended surfactant might solubilize almost 50 g of hexadecane or ethyl oleate and 15 g of C18 triglyceride 8

Normal Case (Winsor) What is Solubilization? All phase diagrams contain a. in all cases

Normal Case (Winsor) What is Solubilization? All phase diagrams contain a. in all cases 1 / 72 UNICAMP Brazil, November 3, 2009 2 / 72 What is Solubilization? it is the ability of a surfactant to produce a monophasic system containing both oil and water Principles and Recent Advances with