Allylic surfmer

Finally one has to be careful about all the side effects, such as the production of water soluble polymers, the sensitivity of the surfactants to transfer reactions in addition to their main character (the case of allylic surfmers for instance), or the effect of the nonionic surfactants on the Tg of the polymers, which may make coalescence of the particles easier. 

The second alternative for polymerizable surfactants is polymeric surfactants. The subject has been recently reviewed by Lachewsky [8]. Even more recently the same authors [135] compared polymerizable surfactant and their homopolymers (polysoaps) and showed that good results can be obtained from them. The same conclusion has been shown valid for the homopolymer of one of the first commercially available allylic surfmers [136]. Recently, core-shell particles have been prepared using an inisurfmer, containing both a polymerizable moiety and a peroxydic group. This compound has been used to cover a seed polymer particle and initiate, from the peroxide group, the polymerization of a shell of another polymer [137]. 

Maleate Surfmers. Surfmers with allylic, acrylic and vinylic moieties tend to homopoly-merize and produce water-soluble polyelectrolytes if used above their CMC. This has shifted researchers attention to maleic derivatives that do not homopolymerize at normal temperatures because their ceiling temperature is too low. Tauer and co-workers have pioneered the synthetic work [4,15] which led originally to compounds like those given in Figure 6.49. An example of maleic-derived Surfmer used in emulsion polymerization lattices is reported in [16] and the advantages provided in commercial paint formulations are discussed later. 

The maleic Surfmers were tested in core-shell emulsion polymerization of styrene/butyl acrylate in comparison with a standard nonreactive surfactant (nonyl phenol reacted with 30 mol of EO - NP30). While the methacrylic-derived Surfmer was completely incorporated during the polymerization (although about one-third of it was buried inside the particles) the NP30, the maleic Surfmer and the allylic and vinyl Surfmers were not incorporated and could be extracted with acetone (for the last two probably because of the formation of acetone-extractable oligomers due to a chain transfer behavior) [31]. 

The oldest report we know dealing with the polymerization of a molecule nowadays termed a surfmer is the work of Bistline et al. [31]. They obtained surface-active polymers with a mean degree of polymerization of about 10 by polymerization of allylic esters of sodium salts of a-sulfostearic acid and a-sulfopalmitic acid. 

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