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RADICAL CHAIN POLYMERIZATION in NET Encode pdf417 2d Various methods are employed for the experimental evaluation of the nitiator ef ciency (These methods are generally also applicable to determining f for photopolymerization) One method involves the determination and comparison of both the initiator decomposition and the production of polymer molecules The initiator decomposition is best determined during an actual polymerization Independent measurement of initiator decomposition in the absence of monomer can give erroneous results The rates of decomposition of initiator can be quite different for pure initiator as compared to initiator in the presence of monomer, since f varies with monomer concentration Also in some cases monomer is involved in the initiation step [eg, molecule-induced homolysis (Eq 3-35), certain redox initiations described in Sec 3-4b-1] AIBN decomposition can be followed relatively easily by following the evolution of nitrogen.

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Measurement of the polymer number-average molecular weight allows a determination of f by comparison of the number of radicals produced with the number of polymer molecules obtained This method requires a knowledge of whether termination occurs by coupling or disproportionation, since the former results in two initiator fragments per polymer molecule and the latter in only one The occurrence of induced decomposition must be taken into account in calculating the number of radicals produced Induced decomposition is negligible for azonitriles but occurs to an appreciable extent with many peroxides The second method is a variation of the rst in which the number of initiator fragments in the polymer is determined by direct analysis of the polymer end groups The analysis is relatively dif cult to perform accurately because of the low concentration of the end groups For a 50,000-molecular-weight polymer, the end groups constitute only $01% of the total.

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