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Simultaneously, the dependence of N on Ri deviates markedly from that expressed by Eq 4-11 When extensive radical desorption occurs, the large fraction of nucleation is initiated by desorbed radicals with the result that N is little affected by Ri Thus, the order of dependence of N on S is 064 for styrene, 086 for methyl methacrylate, 10 for vinyl chloride, and 10 for vinyl acetate, while the orders of dependence on Ri are 036, 020, 0, and 0, respectively [Hansen and Ugelstad, 1979a,b] The emulsion copolymerization of acrylonitrile and butyl acrylate shows a decrease in the exponent of the dependence of N and S from 067 to 040 with increasing surfactant concentration when an anionic surfactant was used [Capek et al, 1988] The exponent was close to one for polymerization in the presence of a cationic surfactant.

Anomolous results have been observed in some emulsion polymerizations inverse dependencies of N, Rp , and X n on surfactant concentration Some surfactants act as inhibitors or retarders of polymerization, especially of the more highly reactive radicals from vinyl acetate and vinyl chloride [Okamura and Motoyama, 1962; Stryker et al, 1967] This is most apparent with surfactants possessing unsaturation (eg, certain fatty acid soaps) Degradative chain transfer through allyl hydrogens is probably quite extensive The polymer particles decrease in stability during intervals II and III since the total polymer particle surface area increases and the coverage of the surface with surfactant decreases The relative decrease in particle stability appears to be insuf cient to cause coalescence as long as stirring is maintained since N is generally observed to be constant.

3:15

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In some systems, however, the stability decreases suf ciently to cause the particles to coalesce and N decreases with conversion [Blackley, 1975] 4-3 OTHER CHARACTERISTICS OF EMULSION POLYMERIZATION 4-3a Initiators.

public class SomeContainerClass : ISupportInitialize { private List<string> m_Data = null; private bool m_Initializing = false; private List<string> m_TempData = null; public List<string> StringCollection { get { return m_Data; } set { if (m_Initializing) m_TempData = value; else m_Data = value; } }

where the summation is extended over all parameters of the set 1; 2; . . . ; p into clusters of at least two points according to (3.11b). From (3.11) it follows that for a centered Gaussian random function, all correlation functions except the second order one vanish. A graphic representation in terms of Mayer diagrams described in [1 4] may be helpful. The correlation function h r1 ; r2 ; . . . ; rp is represented by a set of p points connected by p lines:

The initiators used in emulsion polymerization are water-soluble initiators such as potassium or ammonium persulfate, hydrogen peroxide, and 2,20 -azobis(2-amidinopropane) dihydrochloride. Partially water-soluble peroxides such a succinic acid peroxide and t-butyl hydroperoxide and azo compounds such as 4,40 -azobis(4-cyanopentanoic acid) have also been used. Redox systems such as persulfate with ferrous ion (Eq. 3-38a) are commonly used. Redox systems are advantageous in yielding desirable initiation rates at temperatures below 50 C. Other useful redox systems include cumyl hydroperoxide or hydrogen peroxide with ferrous, sul te, or bisul te ion. 4-3b Surfactants

Anionic surfactants are the most commonly used surfactants in emulsion polymerization [Blackley, 1975; Gardon, 1977]. These include fatty acid soaps (sodium or potassium

h(r1, r2 ) =

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stearate, laurate, palmitate), sulfates, and sulfonates (sodium lauryl sulfate and sodium dodecylbenzene sulfonate). The sulfates and sulfonates are useful for polymerization in acidic medium where fatty acid soaps are unstable or where the nal product must be stable toward either acid or heavy-metal ions. Nonionic surfactants such as poly(ethylene oxide), poly (vinyl alcohol) and hydroxyethyl cellulose are sometimes used in conjuction with anionic surfactants for improving the freeze thaw and shear stability of the polymer or to aid in controlling particle size and size distribution. The presence of the nonionic surfactant imparts a second mode of colloidal stabilization, in addition to electrostatic stabilization by the anionic surfactant, via steric interference with the van der Waals attraction between polymer particles. Non-ionic surfactants are also of use where the nal polymer latex should be insensitive to changes in pH over a wide range. Nonionic surfactants are only infrequently used alone, since their ef ciency in producing stable emulsions is less than that of the anionic surfactants. Anionic surfactants are generally used at a level of 0.2 3 wt% based on the amount of water; nonionic surfactants are used at the 2 10% level. Cationic surfactants such as dodecylammonium chloride and cetyltrimethylammonium bromide are much less frequently used than anionic surfactants because of their inef cient emulsifying action or adverse effects on initiator decomposition. Also, cationic surfactants are more expensive than anionic surfactants. Surfactants increase particle number and decrease particle size as their concentration in the initial reaction charge is increased. However, one can use delayed addition of surfactant after nucleation is complete to improve particle stability, without affecting the particle number, size, and size distribution. 4-3c Other Components

h(r1, r2 , r3 ) =

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