Polymer Handbook by Brandru et al

By Brandru et al

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303R(T2T1) Where given by the author, the overall equation for kd in terms of the frequency factor (A) and activation energy (E,) has been included. Thus for any temperature (converted to K) the kd may be calculated: kd = A exp(-E,/RT) Although a wide range of initiators is reported in the tables, the author admits that the compilation is far from complete. There are several purposeful omissions: (a) azo compounds, where the azo group is part of a ring structure - these recombine almost exclusively; (b) compounds that decompose at appreciable rates only above 200 degrees.

2 8 x 1O-3 8 . 42 T(“C) kd (S-l) x x x x x x x x 10-5 10-4 10 -4 1O-4 10-3 10-3 10-2 1O-2 101 101 101 375 375 375 375 375 ’ TABLE 2. O/RT] Refs. 268 268 268 268 268 268 268 268 268 298 298 298 298 180 180 180 180 180 110 110 110 110 110 319 319 319 297 297 297 240 240 240 252 252 252 252 252 252 360 Notes page II - 69; References page II - 70 II/l0 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS TABLE 2. 6 h Refs. 298 298 298 298 45 45 45 45 45 45 45 45 298 298 2 298 342 288 288 184 21 184 341 341 341 341 341 341 233 233 233 233 237 237 237 237 237 21 233 233 233 233 233 233 233 233 233 356 356 340 21 21 339 221 221 221 243 243 243 171 171 171 171 9 8 / : ) ?

Within each table the individual initiators are listed according to the following criteria: 1. Initiators: (a) according to increasing number of carbon atoms; (b) alphabetically (neglecting trivial prefixes), for compounds containing equal number of carbons; (c) miscellaneous initiators are listed alphabetically in Table 7. 2. For each initiator, solvents are listed alphabetically. 3. For a given solvent, all measurements reported by one investigator are listed in a series, with the activation energy listed opposite the lowest temperature.

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