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Some of the primary radicals in the second laser pulse initiate polymerization that proceeds in the second dark period, at the same time that some propagating chains from the rst dark period are propagating for a second dark period The process continues in a similar manner with each laser burst and subsequent dark period Suf cient laser pulses are used so that the amount of polymer produced is suf cient for analysis by size exclusion chromatography The amount of conversion is only about 2 3%, which means that the monomer concentration is essentially constant over the course of the experiment Some propagating chains terminate by normal coupling and/or disproportionation during the dark periods, but most do not Most of the polymer produced consists of propagating chains that have propagated for different multiples of the time of a dark period tp .



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2 3 4

e-i(W+i<)t}

tp is essentially the same as the cycle time because the pulse width is so much shorter than tp Chains propagate for 1tp, 2tp , 3tp , and so on The degree of polymerization for chains terminated by primary radicals is given by.

--::-::-:::---,------,-=

Li ikp M tp 3-165

where Li is the degree of polymerization for chains that have propagated through i cycles. Li is obtained from the SEC measurement of the polymer molecular weight distribution. Figure 3-12 shows a plot of the molecular weight distribution for a polymerization of dodecyl

v2 k 2 -





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Fig. 3-12 Plots of w(log M) (solid plot) and dw(log M)/d log M (dotted plot) versus log M for dodecyl acrylate polymerization at 4 C and 200 bar in 36 wt% CO2 . w is the weight fraction of polymer having molecular weight M. After Beuermann and Buback [2002] by permission of Elsevier, Oxford; an original plot, from which this gure was drawn, was kindly supplied by Dr. S. Beuermann.

(w - iE)2

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acrylate as w log M versus log M [Beuermann and Buback, 2002]. w is the weight fraction of polymer having molecular weight M. (The symbol L is the same as X, used extensively throughout the text. L is used here not to deliberately add confusion, but because it is used almost exclusively in the PLP-SEC literature.) L1 is obtained from the rst point of in ection on the low-molecular-weight side of the major peak of the molecular weight distribution plot. In practice this is most easily determined from the maxima in a differential plot of the molecular weight distribution, dw log M =d log M versus log M, the dotted plot in Fig. 3-12. For this polymerization it is easy to detect not only L1, but also L2 , L3 , and L4 . The detection of several Li values acts as an internal check on the PLP-SEC method. For Fig. 3-12, the kp values calculated from L1 , L2 , and L3 are within 2% of each other; the value from L4 is within 6 7% of the other values. In practice, closeness between kp values from L1 and L2 are considered suf cient to validate the PLP-SEC method. ktr values can be obtained if chain-transfer constants are known from Mayo or CLD plots (Sec. 3-6, Eqs. 3-108, 3-121). ktr;S can be obtained directly from PLP-SEC polymerization by choosing reaction conditions that minimize normal termination, namely, long cycle times, low [I], and high [S]. kt can be obtained directly from PLP-SEC polymerizations using the relationship

v2k 2 -

2-216

+ iE)2

Marvel, 1975; Ueda et al., 1985]. The reaction probably proceeds by a sequence of two nucleophilic reactions: a nucleophilic substitution to form an amine amide (Eq. 2-217) followed by cyclization via nucleophilic addition (Eq. 2-218).

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Then substitute in (2.76) and do the integral by contour integration. 2.4 Redo Problem 2.3 with the delta function in (2.75) replaced by the Lorentzian function

2-217

Ll(x - xo)

2-218

= - (

Polymerization is often carried out as a two-stage melt polymerization. Oxygen is removed from the reaction system by vacuum and the system purged with nitrogen to avoid loss of stoichiometry by oxidation of the tetramine reactant. The reaction mixture is heated to about 290 C in the rst stage with the reaction starting soon after the reactants form a melt (150 C). The high-volume foam produced in this stage is removed, cooled, and crushed to a ne powder. The second-stage reaction involves heating of the powder at 370 390 C under nitrogen.

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