A key for the preparation of polyacrylate-based polyurethane is the synthesis of hydroxyl-terminated polyacrylate. To our knowledge, exactly one hydroxyl group of every polyacrylate chain has not been reported. The hydroxyl-terminated poly(butyl acrylate) (PBA) has been successfully synthesized by degenerative iodine transfer polymerization (DITP) of the n-butyl acrylate (n-BA) using 4,4′-azobis(4-cyano-1-pentanol) (ACPO) and diiodoxylene (DIX) as initiator and chain transfer agent, respectively, and subsequently substituted reaction of the iodine-terminated PBA with β-mercaptoethanol in alkaline condition. The latter reaction was highly efficient, and the terminal iodine at the end of polymer chains were almost quantitatively transformed to a hydroxyl group. 2,2′-Azobis(isobutyronitrile) (AIBN) and ACPO were used as initiators in the DITPs of n-BA. The results demonstrated that they had a significant influence on the terminal groups of the formed polymer chains. The structure, molecular weight, and molecular weight distribution of the hydroxyl-terminated PBA have been studied by 1H, 13C NMR, and GPC results. The components of hydroxyl-terminated PBA were determined by MALDI-TOF MS spectra, and their formation is discussed. The broad molecular weight distribution of the PBA and the difference in the polymerization behaviors from typical living radical polymerization are explained based on the results of 1H NMR and MALDI-TOF MS spectra. The hydroxyl-terminated PBA has been successfully used in the preparation of PBA-based polyurethane dispersions (PUDs). The aqueous PUDs were stable, and based on the DSC results it can be said that the miscibility of hard segments with PBA chains was improved.
Polymers 2018, 10(2), 219