Bulk grafting of poly(styrene‐alt‐maleic anhydride) onto preirradiated polyolefin membranes in supercritical carbon dioxide

To take advantage of the property of supercritical carbon dioxide as both a solvent and swelling agent, the bulk grafting of poly(styrene‐alt‐maleic anhydride) [P(MAH‐alt‐St)] onto preirradiated polyolefin membranes was performed by a combination of γ‐ray‐preirradiation‐induced graft copolymerization and supercritical fluid‐swollen polymerization. The trapped radicals on the polyolefin backbones were uniformly distributed by γ‐ray irradiation under a nitrogen atmosphere. Subsequently, these polymeric trapped radicals initiated the alternating copolymerization of styrene (St) and maleic anhydride (MAH) infused into the swollen polymer matrix with the aid of supercritical CO₂. It was important that the graft copolymers were relatively pure without any contaminants, including homopolymers, monomers, and initiators. The experimental results show that the degree of grafting could be easily controlled. In addition, St/MAH could synergistically promote the bulk grafting process and strongly effect on the alternating trend; this was confirmed by element analysis and differential scanning calorimetry. Soxhlet extraction, X‐ray diffraction, and Fourier transform infrared spectroscopy indicated that the P(MAH‐alt‐St) was covalently bonded to the polymeric backbones. Scanning electron microscopy showed that the alternating graft chains were uniformly dispersed throughout the 5‐mm thickness of the polymer membranes on the nanometer scale. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013