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PROBLEMS 1-1 Show by equations the overall chemical reactions involved in the synthesis of polymers from a. CH2 CH CO2H b.

{E in (x)B In (X) + B in (x)E in (X)} .



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times as there is a greater tendency for capture of precursor particles by polymer particles when the latter concentrations are high Within the overall behavior predicted by Eq 4-11, there is compatibility with the 3-power dependence of N on Ri predicted by Eq 4-10 5 Nonpolar monomers such as styrene, with little tendency toward radical desorption, generally show 3- and 2-power dependencies of N on S and Ri , respectively This result, however, 5 5 cannot be taken to exclude coagulative nucleation since one cannot preclude the exponent of the dependence of N on S being larger and smaller, respectively, than 3 at lower and higher 5 concentrations of surfactant than those studied Monomers such as vinyl acetate and vinyl chloride, which show case 1 behavior, tend to show a dependence of N on S in line with that predicted by Eq 4-11, indicating the presence of coagulative nucleation.

(9.14)





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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.

From (9.13) we find that (9.15)

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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.

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.

(6 dx Us-t(x) = -4

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

1 7r

82 84 86 88 89 90 92 94 95 96 Enter Cell Data Select Cells Faster Data Entry with AutoFill Change the Font and Size Change Number Formats Apply Conditional Formatting Add Columns and Rows Freeze a Column or Row Name a Range Delete Data or Cells

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

roo dk' vac(k) vac(k')

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