Abstract
Chloromethylated polystyrene was reacted with polystyryl anion at −78°C and at 20°C in mixed solvents (good solvent (tetrahydrofuran (THF)—poor solvent (methylcyclohexane)) and in THF. The decrease in the concentration of the living end was measured photometrically by using a reaction apparatus equipped with an optical cell able to work at low temperatures. The coupling reactions at −78°C ceased within about 15 min. However, the number of branches per backbone polymer molecule increased slightly for all times longer than about 20 min at 20°C. One explanation of our results is that the pendant groups were hindered by the grafted polymer chain and the subsequent grafting of the living polymer onto the coupling agent occurred less readily or not at all in some cases, especially when the molecular weight of the polystyryl anion was large and the content of the poor solvent in the reaction mixture was high.
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Ishizu, K., Fukutomi, T. & Kakurai, T. Formation of Multi-Branched Graft Copolymer by Coupling Reaction. Polym J 7, 228–233 (1975). https://doi.org/10.1295/polymj.7.228
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DOI: https://doi.org/10.1295/polymj.7.228