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Kricheldorf and coworkers [2001a,b,c] have stressed that step polymerizations can proceed either with kinetic control or thermodynamic control. Polymerizations under thermodynamic control proceed with an equilibrium between cyclic and linear products. Polymerizations under kinetic control proceed without an equilibrium between cyclic and linear products. The reactions used in most industrial step polymerizations proceed under thermodynamic control, and most frequently the equilibrium favors linear polymerization over cyclization. However, the extent of cyclization, or at least the presence of cyclic products, is not necessarily zero. Although data are not available for a wide range of systems, the total cyclic content in some polymerizations (e.q., polyesteri cation and polyamidation) has been found to be as high as 1 3% [Goodman, 1988; Semlyen, 1986; Zimmerman, 1988]. (The cyclic content in polysiloxanes is higher; see Sec. 2-12f.) The cyclics present in these polymerizations are generally oligomers with little high-molecular-weight cyclics. Most of the cyclic oligomers are not formed by cyclization reactions between end groups of growing linear polymers (Eqs. 2-71, 2-72) [Kricheldorf and Schwarz, 2003; Kricheldorf et al., 2001a,b,c]. The cyclic oligomers are formed mostly by backbiting, which involves an intramolecular (interchange) nucleophilic substitution reaction, for example, the attack of the hydroxyl end group of a polyester chain on one of its ester carbonyl groups



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T(t) =

3-124

-~IYI(t),

The greater transfer constant for carbon tetrabromide compared to the tetrachloride is due to the weaker C bond The low CS value for chloroform compared to carbon tetrachloride is Br explained by C bond breakage in the former The thiols have the largest transfer constants H of any known compounds due to the weak S bond H Two interesting observations are made when the CS values for various compounds are compared in the polymerization of various different monomers The absolute value of the transfer constant for any one compound may change very signi cantly depending on the monomer being polymerized This is clearly seen in Table 3-6, where many of the transfer agents are 1 2 orders of magnitude more active in vinyl acetate polymerization compared to styrene polymerization This effect is a consequence of the greater reactivity of the vinyl acetate propagating radical.





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The chain-transfer constant for any one compound generally increases in the order of increasing radical reactivity The order of radical reactivity is vinyl chloride > vinyl acetate > acrylonitrile > methyl acrylate > methyl methacrylate > styrene > 1,3-butadiene Radical reactivity is discussed in greater detail in Sec 6-3b The order of reactivity of a series of transfer agents usually remains the same irrespective of the monomer when the transfer agents are relatively neutral in polarity However, there are many very signi cant deviations from this generalization for polar transfer agents Table 3-7 shows data for carbon tetrachloride and triethylamine with several monomers The monomers are listed in decreasing order of reactivity for transfer reactions with neutral transfer agents such as hydrocarbons It is apparent that the electron-rich (electron-donor) transfer agent triethylamine has enhanced reactivity with the electron-poor (electron-acceptor) monomers, especially acrylonitrile.

(A25)

The electron-poor (electron-acceptor) transfer agent carbon tetrachloride has enhanced reactivity with the electron-rich (electron-donor) monomers vinyl acetate and styrene and markedly lowered reactivity with the electron-poor monomers The enhancement of chain-transfer reactivity has been postulated [Patnaik et al, 1979; Walling, 1957] as occurring by stabilization of the respective transition states for the transfer.

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ScreenUpdating = false; // Make the process silent excelApplication.DisplayAlerts = false; // Open the workbook that you wish to export to PDF excelWorkbook ...

By default, Outlook opens the Mail component s Inbox folder when you start the program.To start with a different Mail folder or another component, such as Calendar, click the File tab, click Options and click Advanced. Under Outlook Start and Exit, click the Browse button.Then click the component or Mail folder that you want to set as the default component in the Select Folder dialog box and click OK in both dialog boxes to close them.

We can put (A25) in a more explicit form by differentiating in time and using (A23) to eliminate !VI: 1 . (A.26) M(t) = c(k2T(t). The separation constant ( can be chosen at will; it is completely arbitrary. Each particular choice will yield a different set of modes. But if we demand that both X and c/> be normalized, our freedom to choose ( at will is restricted to a phase. In other words, to have

TABLE 3-7 Polar Effects in Chain Transfer a;b;c Chain-Transfer Agent (C2 H5 3 N CCl4 CS 104 ktr CS 104 ktr 2400 0.17 0.26c 0.12 1.8 370 3800 400 1900 7.1 85 760 84 98 0.12

dV c/>*(r) . c/>(r) = 1,

a CS values from Brandrup et al. [1999], Eastmond [1976a,b,c] and are for 60 C unless otherwise noted. b ktr values were calculated from Eq. 3-107 using kp values from Table 3-11. c CS value is at 80 C. The ktr was calculated using the kp value for 60 C.

(A27)

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