Hydrophilic-lipophilic balances nonionic surfactants

In most cases, these active defoaming components are insoluble in the defoamer formulation as weU as in the foaming media, but there are cases which function by the inverted cloud-point mechanism (3). These products are soluble at low temperature and precipitate when the temperature is raised. When precipitated, these defoamer—surfactants function as defoamers when dissolved, they may act as foam stabilizers. Examples of this type are the block polymers of poly(ethylene oxide) and poly(propylene oxide) and other low HLB (hydrophilic—lipophilic balance) nonionic surfactants. 

Figure 6.11 illustrates the difference in surface composition with respect to the surfactant for a polymerizable amide ethoxylate and a conventional nonionic surfactant of similar hydrophilic-lipophilic balance (HLB). Surfactant concentrations at the film-air interface were... 

Emulsifiers. Removing the remover is just as important as removing the finish. For water rinse removers, a detergent that is compatible with the remover formula must be selected. Many organic solvents used in removers are not water soluble, so emulsifiers are often added (see Emulsions). Anionic types such as alkyl aryl sulfonates or tolyl fatty acid salts are used. In other appHcations, nonionic surfactants are preferred and hydrophilic—lipophilic balance is an important consideration. 

Surfactants employed for w/o-ME formation, listed in Table 1, are more lipophilic than those employed in aqueous systems, e.g., for micelles or oil-in-water emulsions, having a hydrophilic-lipophilic balance (HLB) value of around 8-11 [4-40]. The most commonly employed surfactant for w/o-ME formation is Aerosol-OT, or AOT [sodium bis(2-ethylhexyl) sulfosuccinate], containing an anionic sulfonate headgroup and two hydrocarbon tails. Common cationic surfactants, such as cetyl trimethyl ammonium bromide (CTAB) and trioctylmethyl ammonium bromide (TOMAC), have also fulfilled this purpose however, cosurfactants (e.g., fatty alcohols, such as 1-butanol or 1-octanol) must be added for a monophasic w/o-ME (Winsor IV) system to occur. Nonionic and mixed ionic-nonionic surfactant systems have received a great deal of attention recently because they are more biocompatible and they promote less inactivation of biomolecules compared to ionic surfactants. Surfactants with two or more hydrophobic tail groups of different lengths frequently form w/o-MEs more readily than one-tailed surfactants without the requirement of cosurfactant, perhaps because of their wedge-shaped molecular structure [17,41]. 

Particularly useful is the physical classification of surfactants based on the hydrophile-lipophile balance (HLB) system [67,68] established by Griffin [69,70]. More than 50 years ago he introduced an empirical scale of HLB values for a variety of nonionic surfactants. Griffin s original concept defined HLB as the percentage (by weight) of the hydrophile divided by 5 to yield more manageable values ... 

H Schott. Solubility parameter and hydrophilic lipophilic balance of nonionic surfactants. J Pharm Sci... 

Hunter R., S.F., F. Kezdy, The Adjuvant Activity of Nonionic Block Polymer Surfactants I. The Role of Hydrophile-Lipophile Balance, Journal of Immunology. 127, 1244, 1981. 

Bourrel M, Chambu C (1983) The Rules for Achieving High Solubilization of Brine and OU by AmphiphUic Molecules. Soc Petrol Eng J 23 327-338 Kunieda H, Shinoda K (1985) Evaluation of the hydrophile-lipophile balance (HLB) of nonionic surfactants I. Multisurfactant systems. J Colloid Interface Sci 107 107-121 Kahlweit M, Strey R, Eirman P (1986) Search for tricritical points in ternary systems Water-oil-nonionic amphiphile. J Phys Chem 90 671... 

Nonionic surfactants are often characterized in terms of their hydrophile—lipophile balance (HLB) number (see Emulsions). For simple alcohol... 

At low temperature, nonionic surfactants are water-soluble but at high temperatures the surfactant s solubility in water is extremely small. At some intermediate temperature, the hydrophile—lipophile balance (HLB) temperature (24) or the phase inversion temperature (PIT) (22), a third isotropic liquid phase (25), appears between the oil and the water (Fig. 11). The emulsification is done at this temperature and the emulsifier is selected in the following manner. Equal amounts of the oil and the aqueous phases with all the components of the formulation pre-added are mixed with 4% of the emulsifiers to be tested in a series of samples. For the case of an o/w emulsion, the samples are left thermostated at 55°C to separate. The emulsifiers giving separation into three layers are then used for emulsification in order to find which one gives the most stable emulsion. 

Recently, a new class of inhibitors (nonionic polymer surfactants) was identified as promising agents for drug formulations. These compounds are two- or three-block copolymers arranged in a linear ABA or AB structure. The A block is a hydrophilic polyethylene oxide) chain. The B block can be a hydrophobic lipid (in copolymers BRIJs, MYRJs, Tritons, Tweens, and Chremophor) or a poly(propylene oxide) chain (in copolymers Pluronics [BASF Corp., N.J., USA] and CRL-1606). Pluronic block copolymers with various numbers of hydrophilic EO (,n) and hydrophobic PO (in) units are characterized by distinct hydrophilic-lipophilic balance (HLB). Due to their amphiphilic character these copolymers display surfactant properties including ability to interact with hydrophobic surfaces and biological membranes. In aqueous solutions with concentrations above the CMC, these copolymers self-assemble into micelles. 

K. Shinoda and H. Takeda, The effect of added salts in water on the hydrophile-lipophile balance of nonionic surfactants the effect of added salts on the phase inversion temperature of emulsions, J. Colloid Interface Sci. 32 (1970) 642-646. 

H. Schott, Hydrophilic-lipophilic balance and distribution coefficients of nonionic surfactants, J. Pharm. Sci. 60 (1971) 648-649. 

For a constant amount of nonionic surfactant, the interfacial tension at the planar oil-water interface, for the same amounts of oil and water, passes through a minimum when plotted against the hydrophilic-lipophilic balance (HLB). The emulsion stability passes through maxima in the W/O and O/W ranges and through a minimum between the two at the phase inversion point. The minima in the two cases coincide. These observations are explained on the basis of thermodynamics. The stability of macroemulsions can be correlated with the surface excess of surfactant, which also passes through two maxima and a minimum between them [2.11]. 

Nonionic surfactants consist of a -(CH2CH20)n0H or -OH as the hydrophilic group and exhibit a variety of hydrophile-lipophile balances (HLB) which stabilize O/W or W/O emulsions. Unlike anionic and cationic surfactants, nonionic surfactants are useful for oral and parenteral formulations because of their low irritation and toxicity. Based on their neutral nature, they are much less sensitive to changes in the pH of the medium and the presence of electrolytes. The best use of nonionic surfactants is to produce an equally balanced HLB of two nonionic surfactants one... 

The hydrophilicity of nonionic surfactants can be characterized numerically as their hydrophile-lipophile balance (HLB). An HLB value of 3-6 indicates that the compound is a likely W/O emulsifier 7-9, a wetting agent 8-13, an O/W emulsifier 13-15, a detergent and 15-18, a solubilizer (of oil or other nonpolar compounds) in water. The HLB values of some common compounds are presented in Table 34.12.170 An HLB value of 8.0 is shown in Table 34.12 for lecithin, but manufacturers are able to supply modified lecithins with values of2-12. 

Surfactants are organic molecules that possess a nonpolar hydrocarbon tail and a polar head. The polar head can be anionic, cationic, or nonionic. Because of the existence of the two moieties in one molecule, surfactants have limited solubility in polar and nonpolar solvents. Their solubility is dependent on the hydrophile-lipophile balance of their molecular structure. At a critical concentration, they form aggregates in either type of solvent. This colloidal aggregation is referred to as micellization, and the concentration at which it occurs is known as the critical micelle concentration. The term micelle was coined by McBain (7) to designate the aggregated solute. In water or other polar solvents, the micellar structure is such that the hydrophobic tails of the surfactant molecules are clustered together and form the interior of a sphere. The surface of the sphere consists of the hydrophilic heads. In nonpolar solvents, the orientation of the molecules is reversed. 

Tween 80 (also known as At-Plus 109 and Polysorbate 80) is a polyoxyethylene sorbitan monooleate and was obtained from Atlas Chemical Industries, Inc. This nonionic surfactant has an HLB (hydrophile-lipophile balance) of 15.0 and is used as an emulsifier, solubilizer, and dispersant. It was used without further purification at the 0.1% (w/v) level in partitioning and greenhouse herbicidal evaluations as described below. 

For nonionic surfactants, an optimization of the process was achieved by using a similar approach to the so-called Cohesive Energy Ratio (CER) concept developed by Beerbower and Hill for the stability of classical emulsions (H). Its basic assumption is that the partial solubility parameters of oil and emulsifier lipophilic tail and of water and hydrophilic head are perfectly matched. Thus, the Vinsor cohesive energy ratio Ro, which determines the nature and the stability of an emulsion, is directly related to the emulsifier HliB (hydrophile-lipophile balance) by... 

An empirical scale developed for categorizing single-component or mixed (usually nonionic) emulsifying agents, using this principle, is the hydrophile-lipophile balance or HLB scale. This dimensionless scale ranges from 0 to 20 a low HLB (<9) refers to a lipophilic surfactant (oil-soluble) and a high HLB (>11) to a hydrophilic (water-soluble) surfactant. In gen-... 

The amphiphilic nature of nonionic surfactants is often expressed in terms of the balance between the hydrophobic and hydrophilic portions of the molecule. An empirical scale of ffLB (hydrophile-lipophile balance) numbers has been devised (see Chapter 7, section 7.3.2). The lower the ffLB number, the more lipophilic is the compound and vice versa. ffLB values for a series of commercial nonionic surfactants are quoted in Tables 6.7 and 6.8. The choice of surfactant for medicinal use involves a consideration of the toxicity of the substance, which may be ingested in large amounts. The following surfactants are widely used in pharmaceutical formulations. 

Schott, H. (1969) Hydrophile-lipophile balance and cloud points of nonionic surfactants../. Pharm. Sci. 58(12), 1443-1449. 

Kunieda, H. and Shinoda, K. (1985) Evaluation of the hydrophile-lipophile balance (Hlb) of nonionic surfactants. 1. Multisurfactant systems./. Colloid Interface Sci., 107(1), 107-121. 

---