Polystyrenes (PS) with α-bromoethyl groups (PS-CH(CH3) Br) and bromobenzyl groups(PS-CH(Ph) Cl) have been successfully prepared and the former with low substitute degree was used to initiate ATRP of n-butyl aculate (MA)．In order to avoid the crosslinking reaction during the preparation

the following steps were adopted：the acetylation of PS with acetyl chloride

the reduction of acetylated polystyrene(PS-COCH3) with NaBH4

the esterification of α-hydroethylated polystyrene (PS-CH(CH3)OH) with acetyl anhydride and the bromination of α-acetoxylethylated polystyrene(PS-CH(CH3)OCOCH3) with HBr.As for PS-CH(Ph)Cl

PS-CH(Ph)OH was directly chlorinated with SOCl2 Haloalky polystyrenes and the intermediates were characterized by FTIR

1H-NMR

13C-NMR and GPC and their substitution degrees were determined from the integral height of phenyl protons at δ6.54 and that of the corresponding characteristic proton．All the results indicated a complete conversion of different substitute groups in the preparation process Graft polymerization of butyl acrylate (BA) was carried out and gave out poly (styrene-g-butyl acrylate) successfully using PS-CH(CH3) Br with low substitution degree as the ATRP macroinitiator in conjugation with CuBr and bipyridine at low monomer conversion．