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Surface Stability in Liquid-Crystalline Block Copolymers with Semifluorinated Monodendron Side Groups

Cited 113 time in Web of Science Cited 107 time in Scopus
Authors
Xiang, Maoliang; Li, Xuefa; Ober, Christopher K.; Char, Kookheon; Genzer, Jan; Sivaniah, Easan; Kramer, Edward J.; Fischer, Daniel A.
Issue Date
2000-07-12
Publisher
American Chemical Society
Citation
Macromolecules, 2000, 33, 6106
Abstract
Block copolymers with semifluorinated monodendron side groups were synthesized by attachment of a first generation 2- or 3-armed monodendron acid chloride to a hydroxylated poly(styrene-b-1,2/3,4-isoprene). A convergent growth strategy was developed to synthesize the monodendron groups in good yield using an approach that could be extended to higher generation monodendrons. High extents of attachment were achieved despite the steric effects of the bulky monodendron side groups. The resulting polymers formed a smectic B mesophase at room temperature as determined by WAXS data. The transition temperatures, mesophase range, and enthalpy of the smectic B−isotropic transition were all affected by side-group structural factors such as flexible spacer length, mesogen length, and monodendron core. The critical surface tensions of the resulting semifluorinated polymers were as low as 8 mN/m as determined by Zisman analysis. Surface stability of polymer films in a polar liquid environment was strongly dependent on the extent of attachment exhibited by the semifluorinated groups. The monodendron −CF2− helix within 1 nm of the surfaces has a net orientation normal to the surface as measured by near-edge X-ray absorption fine structure (NEXAFS) methods, but the orientational order parameter Shelix is much higher for the 2-armed monodendrons than for the 3-armed monodendrons. In both cases Shelix seems insensitive to monodendron attachment density along the isoprene block. We suggest that packing frustration of the monodendron subunits produces surfaces with spontaneous curvature that differs depending on whether the monodendrons are 2- or 3-armed. The more highly curved surface topology of the 3-armed monodendrons may provide a partial explanation for its decreased orientational order.
ISSN
0024-9297 (print)
1520-5835 (online)
Language
English
URI
https://hdl.handle.net/10371/5742
DOI
https://doi.org/10.1021/ma992111s
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College of Engineering/Engineering Practice School (공과대학/대학원)Dept. of Chemical and Biological Engineering (화학생물공학부)Journal Papers (저널논문_화학생물공학부)
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