Neutron scattering characterization of homopolymers and graft-copolymer micelles in supercritical carbon dioxide
Superficial fluids (SCF) are becoming an attractive alternative to the liquid solvents traditionally used as polymerization media . As the synthesis proceeds, a wide range of colloidal aggregates form, but there has hitherto been no way to measure such structures directly. We have applied small-angle neutron scattering (SANS) to characterize such systems, and although SCF polymerizations are carried out at high pressures, the penetrating power of the neutron beam means that typical cell windows are virtually transparent. Systems studied include polymers soluble in CO2 such as poly(1,1-dihydroperfluorooctyl acrylate) (PFOA), poly(hexafluoropropylene oxide) (PHFPO) and poly(dimethyl siloxane) (PDMS). PFOA has previously  been shown to exhibit a positive second virial coefficient (A2), though for PHFPO, A2 appears to be close to zero (104 A2 ≃ 0±0.2 cm3 g-2 mol). PDMS is soluble on the molecular level only in the limit of dilute solution and seems to form aggregates as the concentration increases (c > 0.01 g cm-3). Typical hydrocarbon polymers are insoluble in CO2, but it has been found that polymerizations may be accomplished via the use of a stabilizer . For example, styrene has been polymerized in CO2 by means of a polystyrene-b-PFOA block copolymer surfactant, which forms micelles in CO2 and is also amenable to SANS characterization. Other amphiphilic surfactant molecules that form micelles include PFOA-g-poly(ethylene oxide) (PFOA-g-PEO) graft copolymers, which swell as the CO2 medium is saturated with water. These systems have been characterized by SANS, by taking advantage of the different contrast options afforded by substituting D2O for H2O. This paper illustrates the utility of SANS to measure molecular dimensions, thermodynamic variables, molecular weights, micelle structures etc. in supercritical CO2.
Chillura-Martino, D; Triolo, R; McClain, JB; Combes, JR; Betts, DE; Canelas, DA; DeSimone, JM; Samulski, ET; Cochran, HD; Londono, JD; Wignall, GD
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