A diblock copolymer of polystyrene-block-poly(2-hydroxyethyl acrylate) (PS-b-PHEA) was synthesized via atom transfer radical polymerization (ATRP) and reacted with cinnamoyl chloride in triethylamine to yield PS-b-(PCEA-co-PHEA) copolymer with photo-cross-linkable poly(2-cinnamoylethyl acrylate) (PCEA) moieties. Then the triblock copolymer of polystyrene-block-poly(2-cinnamoylethyl acrylate-co-2- hydroxyethyl acrylate)-block-poly(gamma-methacryloxypropyltrimethoxysilane) (PS-b-(PCEA-co-PHEA)-b-PMPS) was synthesized via ATRP from PS-b-(PCEA-co-PHEA) copolymer. Using as-prepared triblock copolymer as a macromolecular coupling agent to modify glass fibers, via microbond tests, the interfacial bond strength between pretreated glass fiber and polystyrene was compared before and after copolymer photo-crosslinking. The partially crosslinked block copolymer coupling agent greatly improved the interfacial adhesion of glass fiber-reinforced polystyrene. (C) Koninklijke Brill NV, Leiden, 2011