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Sakai et al, 2001; Ugelstad and Hansen, 1976] Our discussion will be in qualitative terms Case 2: " 0:5 This is the case usually described in texts as applicable to most n emulsion polymerizations It occurs when desorption of radicals does not occur or is negligible compared to the rate of radicals entering particles (absorption) and the particle size is too small, relative to the bimolecular termination rate constant, to accommodate more than one radical Under these conditions, a radical entering a polymer particle is trapped within that particle and undergoes propagation until another radical enters, at which point there is essentially instantaneous termination Any polymer particle will be active half of the time and dormant the other half of the time In other words, at any given moment half of the polymer particles contain one radical and are growing while the other half are dormant.



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exp { [R(())atRt(()) - R(())aRt(())] r}

The number of radicals per particle " averaged over the particles is 05 Case 2 behavior also requires the initiation n rate not be excessively low and negligible termination of radicals in the aqueous phase Systems exhibiting case 2 behavior are often referred to as zero one systems to indicate that a polymer particle contains either zero or one radical at any given moment Case 1: " < 0:5 The average number of radicals per particle can drop below 05 if n radical desorption from particles and termination in the aqueous phase are not negligible The decrease in " is larger for small particle sizes and low initiation rates n Case 3: " > 0:5 Some fraction of the polymer particles must contain two or more n radicals per particle in order for " to be larger than 0.





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EDIT: Oops, looks like you do have to have office installed. One of the comments in the second link mentions using OpenXmlPowerTools.

Select the cells comprising the range that you want to name. Click the Formulas tab on the Ribbon. Click the Define Name button. The New Name dialog box opens.

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5, since there will always be a n fraction (a very signi cant fraction) that has zero radical per particle This occurs if the particle size is large or the termination rate constant is low while termination in the aqueous phase and desorption are not important and the initiation rate is not too low Although many texts indicate that case 2 is the predominant behavior for all monomers, this is not true Monomers with high water solubility and signi cant desorption of radicals from polymer, such as vinyl acetate, vinyl chloride, and vinylidene chloride, follow case 1 behavior under a variety of reaction conditions [Blackley, 1975; Nomura and Harada, 1981; Sakai et al, 2001] For example, " is approximately 01 or lower for vinyl acetate and vinyl n chloride [Gilbert and Napper, 1974; Litt et al, 1970] Values of " are calculated from Eq.

(4.18)

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4-5 n using the kp value from bulk polymerization at the appropriate percent conversion, that is, at the conversion corresponding to the volume fraction of monomer in the polymer particles The monomers that show strong case 1 behavior are those with high monomer chain-transfer constants Chain transfer to monomer results in a small-sized monomer radical that can desorb from the polymer particle much more readily than the large-sized propagating radical This was veri ed by carrying out emulsion polymerizations with intermittent ionizing radiation The polymerization rate decays to zero after irradiation ceases but before all of the monomer has polymerized [Lansdowne et al, 1980; Ley et al, 1969; Sundari, 1979] If desorption of monomer radicals did not occur, polymerization should continue until monomer would be exhausted The polymerization rate decays for all monomers but at very different rates.

The operator D(a) was introduced by Glauber, and in view of (4.6), it is called the Glauber displacement operator. From (4.7) and (4.18), we find that

The decay rate, which follows the desorption rate, increased as the monomer chain transfer constant increased The effect of reaction conditions on " (and Rp , of course) can be observed even with styrn ene, which shows a very strong tendency toward case 2 behavior under a wide range of reaction conditions [Brooks and Qureshi, 1976; Hawkett et al, 1980] Seed polymerization.

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