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

No matter what the polymerization manner was, polystyrene with unique high T-m (T-m = 170-285 degreesC) was obtained through polymerization of styrene if the amount of BDE/CuCl catalyst was highly increased (mol ratio: St:CuC l = 25:1-2.5:1), Partial crystallinity of the PSt was observed by character izations of X-ray diffraction and DSC. Spectra of H-1-NMR and C-13-NMR show ed that syndiotactic structure contained in the obtained PSt was 5% more th an that in aPSt (atactic polystyrene). According to the proposed "coordinat ed radical cage" mechanism, the coordinated state between radical and catal yst center metal Cu should be more closely packed with increasing the BDE/C uCl catalyst amount, which was induced to partial stereospecific polymeriza tion in the coordinated radical polymerization of St.