Abstract
Exceptionally fast and quantitative synthesis of star-shaped poly(p-methoxystyrene) [poly(pMOS)] with a well-defined structure was achieved using the one-pot “arm-first” polymer-linking method through base-assisting living cationic polymerization. Star polymers with low polydispersity (Mw/Mn ∼ 1.3) were obtained in a short period of time (homopolymerization time ≤ 0.5 min, polymer-linking time ≤ 3 min) by the reaction of living poly(pMOS) (DP = 48–285) with an analogous divinyl compound using EtAlCl2/SnCl4 dual catalysts in CH2Cl2 in the presence of ethyl acetate. The structure of the divinyl compounds and the reaction conditions used for the linking reactions are key to the highly controlled quantitative synthesis. The effect of the arm-chain length of the star-shaped polymer on their thermal properties, evaluated by differential scanning calorimetry, differed from that of the linear polymers. The morphology of the individual star-shaped polymers was also investigated using atomic force microscopy.
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