Synthesis of polystyrene with high melting temperature through BDE/CuCI catalyzed polymerization

No matter what the polymerization manner was, polystyrene with unique high Tm (Tm = 170-285℃) was obtained through polymerization of styrene if the amount of BDE/CuCI catalyst was highly increased (mol ratio: St:CuCI = 25 :12.5 :1). Partial crystallinity of the PSt was observed by characterizations of X-ray diffraction and DSC. Spectra of 1H-NMR and 13C-NMR showed that syndiotactic structure contained in the obtained PSt was 5% more than that in aPSt (atactic polystyrene). According to the proposed "coordinated radical cage" mechanism, the coordinated state between radical and catalyst center metal Cu should be more closely packed with increasing the BDE/CuCI catalyst amount, which was induced to partial stereospecific polymerization in the coordinated radical polymerization of St.