Purification, Surface Tensions, and Miscibility Gaps of Alkyldimethyl and Alkyldiethylphosphine Oxides
Tóm tắt
Alkyldimethyl (C
n
DMPO) with chain lengths of n = 8 (octyl), 10 (decyl), 12 (dodecyl), and 14 (tetradecyl) as well as alkyldiethyl (C
n
DEPO) phosphine oxides with chain lengths of n = 10, 12, and 14 were synthesized and purified to study how the adsorption properties and the location of the miscibility gap of these surfactants depend on the size of the head group and on the length of the alkyl chain. After surfactant purification, the surface tension isotherms were determined from which the cmc, the minimum surface tension σcmc, the maximum surface concentration Γmax, and the minimum surface area A
min were obtained. As expected, for one homologous series, a decrease in the cmc and an increase in Γmax was observed with increasing alkyl chain length. For two surfactants of the same alkyl chain length, the cmc values of the C
n
DEPO surfactants are approximately two times lower than those of the C
n
DMPO surfactants. However, the Γmax values of C
n
DEPO are lower than those of C
n
DMPO as two ethyl chains are sterically more demanding than two methyl chains. In addition to the adsorption properties, the location of the miscibility gap as a function of the alkyl chain length and the head group size was studied. Its location depends on the total number of carbon atoms and not primarily on the length of the main alkyl chain. This observation reflects the decreasing water solubility which can be tuned by increasing the length of either the main alkyl chain or of the shorter head group chains.
Tài liệu tham khảo
Kosolapoff GM, Watson RM (1951) The anhydrides of di-normal-propyl-phosphinic and di-normal-butyl-phosphinic acids. J Am Chem Soc 73:4101
Laughlin RG (1994) The aqueous phase behavior of surfactants. Academic, London
Pospischil KH (1986) Phase-behavior of ternary-systems-H2O-oil-nonionic amphiphile with N-alkyldimethylphosphine oxides. Langmuir 2:170
Sottmann T, Strey R (2005) Microemulsions. In: Lyklema J (ed) Soft Colloids V—Fundamentals in Interface and Colloid Science. Elsevier, Amsterdam, p 5.1
Eskuchen R, Nitsche M (1997) Technology and production of alkyl polyglycosides. In: Hill K, Rybinski Wv, Stoll G (eds) Alkyl polyglycosides: technology, properties and applications. Wiley-VCH-Verlag GmbH, p 9
Rosen MJ (2004) Surfactants and interfacial phenomena. In: Surfactants and interfacial phenomena. Wiley-Interscience, New York, p 20
Aksenenko EV, Makievski AV, Miller R, Fainerman VB (1998) Dynamic surface tension of aqueous alkyl dimethyl phosphine oxide solutions. Effect of the alkyl chain length. Colloid Surf A-Physicochem Eng Asp 143:311
Dudnik V, Lunkenheimer K (2000) Dynamic surface potential and adsorption kinetics of nonionic surfactants at the air–water interface. Langmuir 16:2802
Fainerman VB, Miller R, Möhwald H (2002) General relationships of the adsorption behavior of surfactants at the water/air interface. J Phys Chem B 106:809
Fang JP, Wantke K-D, Lunkenheimer K (1995) Evaluation of the dynamic surface-tension of alkylphosphine oxides. J Phys Chem 99:4632
Lunkenheimer K, Haage K, Hirte R (1999) Novel results on the adsorption properties of n-alkyldimethylphosphine oxides at the air/water interface. Langmuir 15:1052
Lunkenheimer K, Haage K, Miller R (1987) On the adsorption properties of surface chemically pure aqueous-solutions of normal-alkyl-dimethyl and normal-alkyl-diethyl phosphine oxides. Colloid Surf 22:215
Makievski AV, Grigoriev DO (1998) Adsorption of alkyl dimethyl phosphine oxides at the solution/air interface. Colloid Surf A-Physicochem Eng Asp 143:233
Fainerman VB, Miller R, Kovalchuk VI (2003) Influence of the two-dimensional compressibility on the surface pressure isotherm and dilational elasticity of dodecyldimethylphosphine oxide. J Phys Chem B 107:6119
Fruhner H, Wantke K-D, Lunkenheimer K (2000) Relationship between surface dilational properties and foam stability. Colloid Surf A-Physicochem Eng Asp 162:193
Kovalchuk VI, Krägel J, Makievski AV, Loglio G, Ravera F, Liggieri L, Miller R (2002) Frequency characteristics of amplitude and phase of oscillating bubble systems in a closed measuring cell. J Colloid Interface Sci 252:433
Noskov BA, Alexandrov DA, Miller R (1999) Dynamic surface elasticity of micellar and nonmicellar solutions of dodecyldimethyl phosphine oxide. Longitudinal wave study. J Colloid Interface Sci 219:250
Noskov BA, Grigoriev DO, Miller R (1997) Dynamic surface properties of solutions of phosphine oxides: a capillary wave study. J Colloid Interface Sci 188:9
Wantke K-D, Fruhner H (2001) Determination of surface dilational viscosity using the oscillating bubble method. J Colloid Interface Sci 237:185
Wantke K-D, Fruhner H, Fang JP, Lunkenheimer K (1998) Measurements of the surface elasticity in medium frequency range using the oscillating bubble method. J Colloid Interface Sci 208:34
Herrmann KW, Brushmiller JG, Courchene WL (1966) Micellar properties and critical opalescence of dimethyalkylphosphine oxide solutions. J Phys Chem 70:2909
Herder CE (1991) Interaction between phosphine oxide surfactant layers adsorbed on hydrophobed mica. J Colloid Interface Sci 143:1
Pettersson A, Rosenholm JB (2002) Adsorption of alkyldimethylamine and alkyldimethylphosphine oxides at curved aqueous solution/silica interfaces, studied using microcalorimetry. Langmuir 18:8436
Pettersson A, Rosenholm JB (2002) Streaming potential studies on the adsorption of amphoteric alkyldimethylamine and alkyldimethylphosphine oxides on mesoporous silica from aqueous solution. Langmuir 18:8447
Frank C, Sottmann T, Stubenrauch C, Allgaier J, Strey R (2005) Influence of amphiphilic block copolymers on lyotropic liquid crystals in water-oil-surfactant systems. Langmuir 21:9058
Kahlweit M, Strey R, Firman P (1986) Search for tricritical points in ternary-systems—water oil nonionic amphiphile. J Phys Chem 90:671
Blunk D, Bierganns P, Bongartz N, Tessendorf R, Stubenrauch C (2006) New speciality surfactants with natural structural motifs. New J Chem:1705
Hays HR (1968) Reaction of diethyl phosphonate with methyl and ethyl Grignard reagents. J Org Chem 33:3690
Laughlin RG (1965) Synthesis of unsymmetrical aliphatic phosphine oxides via diphenyl alkylphosphonates and Grignard reagents. J Org Chem 30:1322
Sehabi M (2003) Diploma thesis, Universität zu Köln
Lang JC, Morgan RD (1980) Non-ionic surfactant mixtures.1. Phase-Equilibria in C10E4-H2O and Closed-Loop Coexistence. J Chem Phys 73:5849
Schubert KV, Strey R, Kahlweit M (1991) A new purification technique for alkyl polyglycol-ethers and miscibility gaps for water C i E j . J Colloid Interface Sci 141:21
Schubert K-V, Strey R, Kahlweit M (1991) Progr Colloid Polym Sci 84:103
Stubenrauch C, Schlarmann J, Sottmann T, Strey R (2001) Purification of nonionic alkyl polyglycolether (C i E j ) surfactants: the “Inverse” 3PHEX technique. J Colloid Interface Sci 244:447
Kresheck G (1975) Water: a comprehensive treatise. Plenum, New York
Strey R (1996) Water-nonionic surfactant systems, and the effect of additives. Ber Bunsen-Ges Phys Chem Chem Phys 100:182
Holmberg K, Jönsson B, Kronberg B, Lindman B (2003) Model surfaces and methods to determine adsorbtion. In: Surfactants and polymers in aqueous solution. Wiley, West Sussex, p 359
Lunkenheimer K, Malysa K, Wantke K-D (1998) A remark on the dependence of foam lamella stability on the geometric structure of phosphine oxide surfactants. Colloid Surf A-Physicochem Eng Asp 143:403
Laughlin RG (1991) Fundamentals of the Zwitterionic Hydrophilic Group. Langmuir 7:842
