Steric adsorbed polymeric surfactants

Interaction between Oil or Water Droplets Containing an Adsorbed Polymeric Surfactant Steric Stabilisation... 

It is noteworthy that a basic assumption made in the derivation of the free radical desorption rate constant is that the adsorbed layer of surfactant or stabilizer surrounding the particle does not act as a barrier against the molecular diffusion of free radicals out of the particle. Nevertheless, a significant reduction (one order of magnitude) in the free radical desorption rate constant can happen in the emulsion polymerization of styrene stabilized by a polymeric surfactant [42]. This can be attributed to the steric barrier established by the adsorbed polymeric surfactant molecules on the particle surface, which retards the desorption of free radicals out of the particle. Coen et al. [70] studied the reaction kinetics of the seeded emulsion polymerization of styrene. The polystyrene seed latex particles were stabilized by the anionic random copolymer of styrene and acrylic acid. For reference, the polystyrene seed latex particles stabilized by a conventional anionic surfactant were also included in this study. The electrosteric effect of the latex particle surface layer containing the polyelectrolyte is the greatly reduced rate of desorption of free radicals out of the particle as compared to the counterpart associated with a simple... 

Most dispersion polymerizations in C02, including the monomers methyl methacrylate, styrene, and vinyl acetate, have been summarized elsewhere (Canelas and DeSimone, 1997b Kendall et al., 1999) and will not be covered in this chapter. In a dispersion polymerization, the insoluble polymer is sterically stabilized as colloidal polymer particles by the surfactant that is adsorbed or chemically grafted to the particles. Effective surfactants in the dispersion polymerizations include C02-soluble homopolymers, block and random copolymers, and reactive macromonomers. Polymeric surfactants for C02 have been designed by combining C02-soluble (C02-philic) polymers, such as polydimethylsiloxane (PDMS) or PFOA, with C02-insoluble (C02-phobic) polymers, such as hydrophilic or lipophilic polymers (Betts et al., 1996, 1998 Guan and DeSimone, 1994). Several advances in C02-based dispersion polymerizations will be reviewed in the following section. 

Polymers are also essential for the stabilisation of nonaqueous dispersions, since in this case electrostatic stabilisation is not possible (due to the low dielectric constant of the medium). In order to understand the role of nonionic surfactants and polymers in dispersion stability, it is essential to consider the adsorption and conformation of the surfactant and macromolecule at the solid/liquid interface (this point was discussed in detail in Chapters 5 and 6). With nonionic surfactants of the alcohol ethoxylate-type (which may be represented as A-B stmctures), the hydrophobic chain B (the alkyl group) becomes adsorbed onto the hydrophobic particle or droplet surface so as to leave the strongly hydrated poly(ethylene oxide) (PEO) chain A dangling in solution The latter provides not only the steric repulsion but also a hydrodynamic thickness 5 that is determined by the number of ethylene oxide (EO) units present. The polymeric surfactants used for steric stabilisation are mostly of the A-B-A type, with the hydrophobic B chain [e.g., poly (propylene oxide)] forming the anchor as a result of its being strongly adsorbed onto the hydrophobic particle or oil droplet The A chains consist of hydrophilic components (e.g., EO groups), and these provide the effective steric repulsion. 

As most nanoemulsions are prepared using nonionic and/or polymeric surfactants, it is necessary to consider the interaction forces between droplets containing adsorbed layers (steric stabilisation). As this was described in detail in Chapter 10, only a summary will be given here [15, 16]. 

The fact that poloxamers and proteins were excellent steric stabilizers for double emulsions encouraged scientists to try and design an optimal synthetic polymeric emulsifier to be adsorbed both at the internal and the external interfaces. However, only few commercial polymeric surfactants are available, many of which are designed for... 

A-B, A-B-A block and BAn graft type polymeric surfactants are used to stabilise emulsions and suspensions [18]. B is the anchor chain that adsorbs very strongly at the 0/W or S/L interface, whereas the A chains are the stabilising chains that provide steric stabilisation. These polymeric surfactants exhibit surface activity at the 0/W or S/L interface. The adsorption and conformation of these polymeric surfactant at the interface has been described in detail in reference 18. 

The inherently high colloid stability of nanoemulsions when using polymeric surfactants is due to their steric stabilization. The mechanism of steric stabilization was discussed above. As shown in Fig. 1.3 (a), the energy-distance curve shows a shallow attractive minimum at separation distance comparable to twice the adsorbed layer thickness 28. This minimum decreases in magnitude as the ratio between adsorbed layer thickness to droplet size increases. With nanoemulsions the ratio of adsorbed layer thickness to droplet radius (8/R) is relatively large (0.1 0.2) when compared with macroemulsions. This is schematically illustrated in Fig. 1.28 which shows the reduction in with increasing 8/R. 

Steric repulsion results from the presence of adsorbed layers of surfactants and/or polymers. The use of natural and synthetic polymers (referred to as polymeric surfactants) for stabilization of suspension concentrates and emulsions (EW s) plays an important role in agrochemical formulations. Polymers are particularly important for preparation of concentrated dispersions, i.e. at high volume fraction ( j of the disperse phase,... 

As an indirect method toward processability, conducting colloids of polypyrrole and polyaniline have been prepared via a dispersion polymerization route. In this approach, the conducting polymer is che-mically synthesized in the presence of a suitable polymeric surfactant. The surfactant adsorbs or is chemically grafted onto the conducting polymer particle or chain and prevents macroscopic precipitation by a steric stabilization mechanism. The result is a stable dispersion of submicronic conducting polymer particles which consist of a conducting core and a thin outer layer of the non conducting surfactant as shown schematically in Fig. 2. 

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