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For comparison, PI has a solubility parameter of 17.0.
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For comparison, PI has a solubility parameter of 17.0.
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h values measured at 90°. The data do not reflect the real lengths and radii of the micelles. TEM provide direct measurement of the micellar lengths.
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h values measured at 90°. The data do not reflect the real lengths and radii of the micelles. TEM provide direct measurement of the micellar lengths.
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48
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34247843445
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In a separate experiment, we found that the crystallinity of PFS thin films can be improved by annealing under an atmosphere of a good solvent
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In a separate experiment, we found that the crystallinity of PFS thin films can be improved by annealing under an atmosphere of a good solvent.
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49
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34247865282
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We explored several methods for the cross-linking reactions and encountered setbacks for most reactions. For example, free radical reactions led to insurmountable intermicellar cross-linking. Vulcanization of PI corona using S2Cl2 avoided intermicellar cross-linking but caused oxidation of the PFS core of the micelles. Attempted olefin metathesis using a commercially available Ru catalyst was also unsuccessful, presumably due to the poor solubility of the catalyst in hexanes
-
2 avoided intermicellar cross-linking but caused oxidation of the PFS core of the micelles. Attempted olefin metathesis using a commercially available Ru catalyst was also unsuccessful, presumably due to the poor solubility of the catalyst in hexanes.
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50
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34247896109
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As mentioned by a reviewer, for a difunctional cross-linker, the presence of an excess of cross-linker should decrease the extent of cross-linking due to the stoichiometric imbalance (assuming equal functional group reactivity, the degree of cross-linking should drop by a factor of 4 when 2 equiv of the cross-linker are used). However, we observed an increase in the degree of cross-linking when an excess of cross-linker is used. We presume that this is a result of the unequal reactivity of the two ends of the cross-linker: once one end reacts, the second end reacts much faster due to its close proximity to the Pt catalyst and the neighboring vinyl groups in the micelle.
-
As mentioned by a reviewer, for a difunctional cross-linker, the presence of an excess of cross-linker should decrease the extent of cross-linking due to the stoichiometric imbalance (assuming equal functional group reactivity, the degree of cross-linking should drop by a factor of 4 when 2 equiv of the cross-linker are used). However, we observed an increase in the degree of cross-linking when an excess of cross-linker is used. We presume that this is a result of the unequal reactivity of the two ends of the cross-linker: once one end reacts, the second end reacts much faster due to its close proximity to the Pt catalyst and the neighboring vinyl groups in the micelle.
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51
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Apparently the micelles pin to the substrate surface while solvent evaporation occurs for the TEM measurement, enabling the swelling behavior to be examined. It is likely nevertheless that some size contraction occurs under these conditions
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Apparently the micelles pin to the substrate surface while solvent evaporation occurs for the TEM measurement, enabling the swelling behavior to be examined. It is likely nevertheless that some size contraction occurs under these conditions.
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