Comb-like hydroxyl functionalized atactic polystyrene was synthesized using the catalytic system (n-BuCp)2TiCl2/Sn/Is via living radical polymerization with Sn as the reducing agent and poly\|［(phenylglycidyl ether)-co-formaldehyde］ (Is) as the initiator.The effect of polymerization conditions

such as temperature

time

as well as the ratio of initiator to monomer on the polymerization performance was investigated.The catalytic active center was stable at the temperature range of 65～95℃

and the propagation rate increased with temperature.The structure and the properties of the obtained polymer were characterized by GPC

13C-NMR

WAXD and 1H-NMR.The GPC result indicated that a linear dependence of Mn on the monomer conversion was observed in each case

and the resulting polymer exhibited a rather low polydispersity (Mw/Mn=1.6～1.9) even the polymerization time (6

8

12

16

18 h) or the ratio of initiator to monomer (［Is］/［St］ = 1/250

1/500

1/750) had been changed

which confirmed that living radical polymerization characters prevailed in the polymerization process.The results of 13C-NMR and WAXD suggested that the polymer is featured by an atactic structure.The 1H-NMR results showed that the polymer molecules possessed hydroxyl groups

and the number of arms in each polymer molecule was in good agreement with the number of epoxy functional groups in the initiator (Is)

which indicated the radicals derived from ring opening reaction of epoxide were the active species for living radical polymerization of styrene.