New chelating glucose-based surfactants

Size: px

Start display at page:

Download "New chelating glucose-based surfactants"

Oswald Dalton
6 years ago
Views:

1 New chelating glucose-based surfactants Nadège FERLIN Laboratoire des Glucides UMR 6219 Université de Picardie Jules VERNE AMIENS A Greener Chemistry for Industry 2 au 5 octobre 2007 Villeneuve d Ascq

2 I. GENERAL : Heavy metals pollution In France, more than 3800 sites are polluted by heavy metals Pollution due to human activities Cause environmental and health problems To treat : Biological treatements : phytoremediation Permeabilisation Physical and chemical treatments : oxido-reduction, precipitation, extractions, flotation

3 I. GENERAL : Flotation Evacuate metallic pollutants of an aqueous phase with surfactants and an air bubbling Surfactant : Amphiphilic molecule Hydrophilic moiety: Polar head ionic or non-ionic Hydrophobic moiety Carbon chain Adsorption at the interfaces then formation of micelles : decrease superficial and interfacial tensions, detergency, emulsion, foaming, What about flotation? Adding of surfactants R S Polluted water R R N S- S S- Adsorption Air bubbling Evacuation of pollutants with the foam

4 I. GENERAL : Chelating Surfactant Koide et al. X X X = C, S 3 - R N 2 R N N R N N X H 2 N - 3 S Uranium s flotation Bull. Chem. Soc. Jpn., 56, , (1983) Bull. Chem. Soc. Jpn., 59, , (1986) S 3 - Woller et al. : Quinoline and oxime derivates for liquid-liquid extraction N Sawada et al. : hydrophobically modified EDTA for cosmetic use -C -C N N CR R N R C- Colloid surface A, 117, , (1996) US Patent Application , (2003)

5 In 3 steps : xidation of the primary alcohol II. SYNTHESIS : ur molecules Hydrophilic head (glucose) H N Y R Chelating function Y =, aminoacids skeleton Hydrophobic tail Glycosidation of fatty alcohol Sugar : Good solubility in water, non-toxic Natural and cheap ressources Sugar-based surfactants are known as biogradable and good foaming agents Target : Best efficiency as possible for metal extraction combined with easy, fast and non-expensive reactions

6 II. SYNTHESIS : Glycosidation a) R (2eq), ZnCl 2, µ-waves b) Ac 2, Py ρ = % R MeNa, Me ρ > 90 % R Use of microwaves irradiation : often use in green chemistry No solvent, economy of energies Very fast reactions with good yield Useful with different fatty alcohols R = C n H (2n+1) avec n=6, 8, 10, 12, 16 Control of the anomers ratio

7 II. SYNTHESIS : Glycosidation Control of the anomers ratio % alpha Hexanol ctanol Decanol Dodecanol Hexadecanol reaction time (min) Difficulties to separate the anomers

8 II. SYNTHESIS : xidation Direct oxidation C 8 H 17 C C 8 H 17 TEMP : ρ = 89 % Very long reaction, purification problems 2 /Pt in basic medium : ρ = 36 % Long reaction and expensive xidation on protected glucosides C 8 H 17 a) TrCl, Py b) Ac 2 ρ = 84 % Tr C 8 H 17 Cr 3 cat., H 5 I 6 CH 3 CN/H 2 ρ = 85 % C C 8 H 17 MeNa, Me ρ > 90 % C C 8 H 17

9 II. SYNTHESIS : Coupling Hydroxamic acid Unprotected coumpond C C 8 H 17 Anh Me, H 2 S 4 ρ = 90% CMe C 8 H 17 NH 2 50% aqueous, Me ρ = 73% CNH C 8 H 17 Protected compound C C 8 H 17 MeI, Bu 4 NI KHC 3, anh. DMF ρ = 75% CMe C 8 H 17 NH 2 50% aqueous, Me ρ = 67% CNH C 8 H 17

10 III. INTERFACIAL PRPERTIES Measure the superficial tension depending on the log of the concentration γ CMC critical micellar concentration Log (C) air water ther properties are also determined HLB calculated by modelisation micelle

Difference of pression is proportional to the tension γ = (r/2)*d*g* h Compounds C8α C C8β

11 III. INTERFACIAL PRPERTIES The «capillar» method (Castro et al, J. Chem. Educ., 78, 347, (2001)) Method reposing on Laplace law Capillar in a solution of surfactants Difference of pression is proportional to the tension γ = (r/2)*d*g* h Compounds C8α C C8β C C8 α CNH C8 β CNH CMC (mm) 13,1 ± 1,8 15,6 ± 1,5 20,7 ± 1,3 20,6 ± 2,6 ctyl-α-d-glucopyranoside : 10.0

12 Flotation test IV. METAL EXTRACTIN Mixing of surfactant and metal introduced in a column reliated to a pump air Tested metals : Fe(III), Cu(II), Cd(II), Cr(III), Ni(II), Zn(II) 3 times reapeted Quantification by ICP Use the «adding method» because of the matrix effect of the surfactants

13 III. METAL EXTRACTIN 3.5 Extraction factor 3 Ef = C C metal foam metal liquid Ef Fe Cd Cu C8aC C8bC C8aCNH C8bCNH Visual good results with iron and C8bCNH Initial Residual liquid Foam

14 ACKNWLEGMENTS Laboratoire des Glucides UPJV-AMIENS (France) Pr. José KVENSKY and Dr. Eric GRAND Gaétane SERVANT, Thomas MEYER, Sébastien DAUPHIN and Danavathani KANTHASANY Centro de Estudios Transdiciplinarios del Agua (CETA) Facultad veterinarias de BUENS AIRES (Argentina) Pr. Alicia FERNÀNDEZ-CIRELLI Dr. Mariano CASTR, Carlos JEDA and Diego GRASSI Financial supports: Délegation Générale pour l Armement CNRS - CNICET

15 Thanks for your attention Any questions?

Colloid chemistry. Lecture 10: Surfactants

Colloid chemistry. Lecture 10: Surfactants Colloid chemistry Lecture 10: Surfactants Applications of surfactants: cleaning/detergents (40%); textiles; cosmetics; pharmacy; paint; food; etc. Etymology Surfactant micelles surfactant molecule spherical