Abstract
AbstractThe analysis of the endgroups of the oligomers produced in the styrene (A)–CCl4(S) system (system I), the methyl methacrylate(B)–CCl4 system (system II), and the styrene–methyl methacrylate–CCl4 system (system III) was carried out in order to clarify the mechanism of the initiation, transfer, and termination. In system I, the number of Cl atoms per oligomer molecule NCl increases with the molar ratio of [S]/[A] when the molar ratio of [S]/[A] is below unity and is about four when the molar ratio of [S]/[A] is above unity, and the number of initiator fragments per oligomer molecule NI decreases with the increase in the molar ratio of [S]/[A]. In system II, NCl is about 0.45 over a considerably wide range of the molar ratio of [S]/[B]. In system III, NCl increases and NI decreases with the increase in the molar ratios of [S]/([A] + [B]) and [A]/[B]. From the data of NCl and NI, the fraction ICC14 of the initiation by the tri‐chloromethyl radical in the overall initiation reactions and the fraction TCC14 of the chain transfer reaction of the growing radical of styrene in all the reactions which produce the cooligomer in the system III were calculated. ICCl3 and TCC14 both increase with the molar ratios [S]/([A] + [B]) and [A]/[B].
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