Chitosan （CS） was successfully modified in supercritical carbon dioxide （ scCOz ） by grafting method to enhance its water solubility. In this work, a three.arm star-like fluorinated polymer was synthesized by atom transfer radical polymerization （ ATRP ） method and applied as a surfactant in supereriticul carbon dioxide （scCO2 ）. Then 2-acrylamido-2-methyl propane sulfonie acid （AMPS） was grafted onto CS （CS-g-PAMPS） in H2O/scCO2 inverse emulsion. The effects of mass ratio of water and surfactants （Rw/s ） and pressure of scCO2 on the grafting reaction were investigated. The grafting rate, partide size, and dispersity in water of CS-g-PAMPS varied greatly as Rw/s and pressure of scCO2 changed. It could be found that the value of Rw/s at 12 and the pressure of scCO2 at 30 MPa were the optimum conditions for the grafting reaction. CS-g-PAMPS prepared in this reaction system has higher grafting rate, smaller particle sizes, and better dispersity in water than those prepared via conventional methods.
Dispersion copolymerization of acryionitrile-vinyi acetate （AN-VAc） has been successfully performed in supercriticai carbon dioxide （ScCO2） with a series of iipophilic/CO2-philic diblock copolymers, such as poly（ styrener-acrylonitrile）-b- poly （ 1, 1, 2, 2-tetrahydroperfluorooctyl methacrylate） （PSAN-b-PFOMA）, as steric stabilizers. The structure and the particle morphology of the product were characterised by FT-IR and SEM. In addition, the effects of the stabilizer on the surface properties of the products were investigated in detail. Results indicate that the surface free energy of the poly （AN-r-VAc） （PAVAc） film decreases dramatically because of the existence of the stabilizer. And, when the initial concentration of the monomer was 10% （the mass （g） of monomer to the volume （mL） of ScCO2 ） the optimal concentration of the stabilizer is about 5% （w/w% to monomers）.
The monomer reactivity ratios of free radical copolymerization of styrene and methyl methacrylate in carbon dioxide at vapor-liquid equilibrium state (vlCO(2)) at 65 degrees C and under 7.5-8.5 MPa were measured. The experimental results showed that, in comparison with the data in bulk copolymerization, the monomer reactivity ratio of St in vlCO(2) increased acompanied by a somewhat decrease in that of MMA. Further analysis of the sequence distributions of these copolymers by H-1-NMR spectra indicated that there was a significant bootstrap effect in this system. The local monomer concentrations in the proximity of growing free radicals, rather than the true reactivity of monomers or free radicals, were altered by the presence of vlCO(2), leading to the change in monomer reactivity ratios.
