Poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) [poly(TA-N)] was synthesized in dry benzene using AIBN as an initiator at 60degreesC. The effects of the monomer concentration (C-m), initiator concentration (C-i), and reaction time on the polymerization were investigated. The results of DSC and TGA showed that when the C-i remains constant, the higher the C-m value is, the better the thermal character for the product in the range of experiments. When the reaction was conducted for 30 h, polymerization is almost completed. The C-i should remain lower than 0.25 g/100 g monomer when the C-m is lower than 15 g/L. When the C-m is higher than 15 g/L, the Ci should be increased slightly. When the C remains constant, it was observed that an increase in the C-i increases the yield (mass of polymer after reaction/mass of monomer before reaction). On the other hand, the melting (T-m) and decomposition (T-d) temperatures of the reaction product decrease, except when the C-m reaches 20 g/L and the reaction time is 30 h. High purity CO2 was continuously pumped using a high pressure syringe pump. Rapid expansion of poly(TA-N) in supercritical CO2 happened under control through a porous sintered metal plate. The poly(TA-N) morphology was analyzed with a scanning electron microscope. An amorphous polymer was formed at a preexpansion temperature of 45degreesC. Fibers were formed at temperatures of around 60-80degreesC. An increase of the temperature slightly increases the particle size. At 105degreesC, most of the particles are spheres and dendrites. The corresponding CO2 flow rate upon expansion was 2.5-5.0 +/- 0.3 L/min (STP) and the pressure drop was 2 MPa. At the higher CO2 flow rate, the spheres and dendrites became smaller. (C) 2003 Wiley Periodicals, inc.