, Geoffrey D. Bothun
. (1) Mechanical and Chemical Engineering, North Carolina A&T State University, 1601 E. Market St., Greensboro, NC 27411, (2) Chemical Engineering, North Carolina State University, Raleigh, NC 27695
Supercritical CO
2 is an environmentally responsible solvent with tunable physical properties. A diverse array of polymerizations and polymer processing techniques has been reported using CO
2. Foaming or CO
2 swelling occurs when a polymer is placed in contact with supercritical CO
2. CO
2 swelling can either be used to extract or add materials into a polymeric substance. A high-pressure isothermal calorimetric method has been developed to observe alterations in the glass transition temperature (T
g) of poly(acrylic acid) (PAA) due to the adsorption of gaseous and supercritical CO
2. PAA is a hydrophilic commodity polymer used as a thickener and a water absorbent (e.g. baby diapers). Recently, Liu and coworkers (Liu,T.,Continuous Precipitation Polymerization of Acrylic Acid in Supercritical Carbon Dioxide,2005 ) have demonstrated the ability to synthesize PAA in supercritical CO
2 via continuous precipitation polymerization. Theoretical calculations of CO
2-induced T
g depression, stemming from the amount of CO
2 adsorbed in PAA, suggest that the morphology of PAA particles depend on experimental operating conditions during precipitation polymerization and the proximity of these conditions to T
g. The goal of this project is to evaluate (i) T
g for PAA polymerized in supercritical CO
2 ,(ii) the reduction of T
g for PAA in the presence of CO
2 (20.7 to 206.8 bar), (iii) and the validity of the theoretical model for T
g depression. CO
2-induced T
g depression was investigated in custom designed high-pressure sample cells using a Setaram C80 calorimeter. PAA samples synthesized in supercritical CO
2 (206.8 bar, 50 to 90°C) have a T
g ranging from 114 -120°C, which is analogous to PAA that is produced conventionally by solution polymerization. PAA adsorption of compressed CO
2 yielded a reduction in the T
g to 100°C at 58.7 bar ± 0.6. In the presence of supercritical CO
2 the T
g reduced to 80°C at 126 bar. These reductions in T
g are consistent with theoretical calculations for T
g approximation using the Chow's equation.