| Abstrakt: |
The solubilities of the homopolymers poly(ethylene glycol) (PEG), poly(ethylene glycol) dimethyl ether (PEGDME), and poly(propylene glycol) (PPG) in CO2 were correlated with a lattice fluid hydrogen-bonding (LFHB) model, which was then used to predict solubilities of Pluronic L (PEG-PPG-PEG) and Pluronic R (PPG-PEG-PPG) triblock copolymers. Simple averaging rules were developed to evaluate the physical properties of the copolymers without introducing any adjustable parameters. For a given average molecular weight, the predictions of the model were quite reasonable and in some cases perhaps more accurate than the data, due to the large polydispersity of the samples. The model predicts the effects of total molecular weight, PEG/PPG ratio, terminal functional groups, temperature, and density on solubility. The much higher solubility of PPG versus PEG is due primarily to steric hindrance from the methyl branch, which weakens segment−segment interactions, and to a lesser extent to the stronger hydrogen bond donor strength of a primary (in the case of PEG) versus a secondary (in the case of PPG) alcohol terminal group. Consequently, the predicted solubilities of Pluronic L surfactants, which have stronger hydrogen bond donors on the terminal groups, are not much smaller than those of Pluronic R surfactants for given molecular weights of the blocks. |
