Hydroxyl-terminated linear and star-shaped telechelic polyisobutylene have been successfully synthesized by living cationic polymerization using propylene oxide (PO)/Titanium tetrachloride (TiCl4) as the initiator system. A one-step method to prepare the terminal hydroxyl group was realized by selecting the cheap and beautiful epoxide as the functional initiator, which has the prospect of industrial application. The polymerization mechanism was proposed by the end structure analysis and Gaussian calculation results. At the same time, the living linear macromolecular chain was used as the starting point to react with divinyl compounds for synthesis of star-shaped hydroxyl-terminated polyisobutylene. The effects of initiator-crosslinking agent ratio, arm length, and reaction time on the coupling reaction were studied.
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