Emulsion polymerization steric stabilization

In Sects. 1.2.1 and 1.2.2 we shall first qualitatively consider double layer and Van der Waals interactions, the two contributions to the DLVO potential (Sect. 1.2.3), and then discuss (polymeric) steric stabilization by end-attached polymer in Sect. 1.2.4. While not further discussed here we mention that adsorbing polymers, proteins or particles can also be used to protect colloids against flocculation. For protein adsorption, often used for instance in food emulsions, we refer to [28]. Using particles to stabilize colloids is referred to as Ramsden-Pickering stabilization [29]. Finally, the depletion interaction will be treated in Sect. 1.2.5. 

Kusters et al. [42] showed that the desorption rate constant for monomeric radicals decreases signihcantly, compared to anionic surfactant, in the emulsion polymerization stabilized by n-nonylphenoxypolyethoxy ethanol with an average of 30 ethylene oxide units per molecule. This result implies that there exists a steric barrier surrounding the latex particle that retards the entry (or exit ) of free radicals for the emulsion polymerization system stabilized by nonionic surfactant. More research efforts are required to reconcile this controversial issue. 

Monosized polystyrene particles in the size range of 2-10 /am have been obtained by dispersion polymerization of styrene in polar solvents such as ethyl alcohol or mixtures of alcohol with water in the presence of a suitable steric stabilizer (59-62). Dispersion polymerization may be looked upon as a special type of precipitation polymerization and was originally meant to be an alternative to emulsion polymerization. The components of a dispersion polymerization include monomers, initiator, steric stabilizer, and the dispersion medium... 

Capek I. Sterically and electrosterically stabilized emulsion polymerization. Kinetics and preparation. Adv Colloid Interface Sci 2002 99 77-162. 

A series of amphiphilic diblock macromonomers were successfully used as steric stabilizers in the emulsion polymerization styrene [98]. Copolymerization led to the formation of polymer latexes of high colloidal stability. These... 

The emulsion polymerization process involves the polymerization of liquid monomers that are dispersed in an aqueous surfactant micelle-containing solution. The monomers are solubilized in the surfactant micelles. A water-soluble initiator catalyst, such as sodium persulfate, is added to the aqueous phase. The free radicals generated cause the dispersed monomers to react to produce polymer molecules within the micellar environment. The surfactant plays an additional role in stabilizing dispersion of the produced polymer particles. Thus, the surfactants used both provide micelles to house the monomers and macroradicals, and also stabilize the produced polymer particles [193,790], Anionic surfactants, such as dodecylbenzene sulfonates, are commonly used to provide electrostatic stabilization [193], These tend to cause production of polymer particles having diameters of about 0.1-0.3 pm, whereas when steric stabilization is provided by, for example, graft copolymers, then diameters of about 0.1-10 pm tend to be produced [790,791]. 

Use of macromonomers as reactive (copolymerizable) surfactants in heterogeneous systems such as emulsion and dispersion constitutes an increasingly important application in the design of polymeric microspheres, as will be discussed later in Sect. 6. Here the macromonomers copolymerize in situ with some of the substrate comonomers to afford the graft copolymers, the grafts (branches) of which serve as effective steric stabilizers by anchoring their backbone onto the surfaces of the particles. In general, however, the copolymerization reactivities of macromonomers in such systems are not well understood yet. 

Instead of conventional surfactant molecules, amphiphilic water soluble macromonomers, especially PEO macromonomers, have been used extensively as a reactive emulsifier and as steric stabilizer polymer, as summarized in Table 5. Generally speaking, however, the mechanism for the particle nucleation in the emulsion polymerization systems using macromonomers has been poorly established when compared to the dispersion copolymerizations with macromonomers as mentioned earlier. 

Stability in mixtures of colloidal particles and polymer molecules, dispersed in a solvent, has been the subject of experimental and theoretical investigations for a long time and it has applications in diverse fields such as paint technology, wastewater treatment, emulsion polymerization, biology etc. It has now been well recognized that polymer molecules can be used to induce either stabilization or flocculation (phase separation) in colloidal dispersions. It is important to distinguish between polymers which are adsorbed on the particle surface and those that are free in solution because the two situations usually lead to qualitatively different effects. Stability imparted by adsorbed polymers is known as steric stabilization and the flocculation or phase separation caused by the free polymer is due... 

Surfactants are employed in emulsion polymerizations to facilitate emulsification and impart electrostatic and steric stabilization to the polymer particles. Sicric stabilization was described earlier in connection with nonaqueous dispersion polymerization the same mechanism applies in aqueous emulsion systems. Electrostatic stabilizers are usually anionic surfactants, i.e., salts of organic acids, which provide colloidal stability by electrostatic repulsion of charges on the particle surfaces and their associated double layers. (Cationic surfactants are not commonly used in emulsion polymerizations.)... 

One possibility is to provide the particles with a thin steric barrier such as the "micro hairs which could occur on the surface of a latex solvation of the polymer chain beyond the ionic end group. Indeed some evidence for this occurs with certain laticcs. For example, Smithan et al. (1973) have reported evidence of steric stabilization with polystyrene latices with a high content of carboxyl groups on the surface prepared by an essentially conventional emulsion polymerization method. Microsteric stabilization with latices could be an important factor and this is undoubtedly an area that needs more extensive investigation. 

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