By one-pot technique the copolymerization of styrene with ethylene promoted by a cyclopentadienyl titanium trichloride (CpTiCl3)/1

4-butanediol di glyci dyl ether (BDGE)/Zn catalytic system to yield aPs-b-P(S-co-E)- b-PE block copolym ers was investigatedvia sequential monomer addition strategy in the presenc e of methylaluminoxane (MAO) as cocatalyst for the coordination polymerization stage. The effect of temperature

time

ethylene pressure and the ratio of Al/Ti in mol on the polymerization performance was discussed in detail.Basically

aPs-b-P(S-co-E)-b-PE block copolymers was obtained

togethe r with atactic polyst yrene through the approach

which was determined by solvent extraction.The CHCl3-soluble product was determined by GPC

DSC

WAXD and 13C-NMR.The molecular weig ht distribution (MWD) of the copolymer varied slightly at the range from 1.71 t o 2.11The DSC result showed that the copolymer featured one glass transition te mperature (for example Tg= 86℃) attributed to the Tg of aPs domains an d one melting point (for example Tm= 114℃) attributed to the Tm of PE domains.The blocky microstructure of the copolymer was further confi rmed by WAXD and 13C-NMR.These results indicated that the copolymer was consisted of amorphous aPs segments

P(S-co-E) segments and crystalline PE segmen ts.