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Volumn 129, Issue 17, 2007, Pages 5630-5639

Shell-cross-linked cylindrical polyisoprene-b-polyferrocenylsilane (PI-b-PFS) block copolymer micelles: One-dimensional (1D) organometallic nanocylinders

Author keywords

[No Author keywords available]

Indexed keywords

BLOCK COPOLYMER MICELLES; POLYFERROCENYLSILANE (PFS); POLYISOPRENE (PI) CORONAS;

EID: 34247882658     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja068730f     Document Type: Article
Times cited : (102)

References (58)
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    • (1997) Adv. Mater , vol.9 , pp. 437-439
    • Liu, G.1
  • 25
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    • For work on core-shell cylinders, see
    • (b) For work on core-shell cylinders, see: Djalali, R.; Li, S.-Y.; Schmidt, M. Macromolecules 2002; 35; 4282-4288.
    • (2002) Macromolecules , vol.35 , pp. 4282-4288
    • Djalali, R.1    Li, S.-Y.2    Schmidt, M.3
  • 30
    • 0035941073 scopus 로고    scopus 로고
    • Manners, I. Science 2001, 294, 1664-1666.
    • (2001) Science , vol.294 , pp. 1664-1666
    • Manners, I.1
  • 37
    • 15244347263 scopus 로고    scopus 로고
    • Cylindrical micelles have also been formed from block copolymers with amorphous polyferrocenylsilane blocks. See: (a) Wang, X, Winnik, M. A, Manners, I. Macromolecules 2005, 38, 1928
    • Cylindrical micelles have also been formed from block copolymers with amorphous polyferrocenylsilane blocks. See: (a) Wang, X.; Winnik, M. A.; Manners, I. Macromolecules 2005, 38, 1928.
  • 45
    • 34247853881 scopus 로고    scopus 로고
    • For comparison, PI has a solubility parameter of 17.0.
    • For comparison, PI has a solubility parameter of 17.0.
  • 47
    • 34247870311 scopus 로고    scopus 로고
    • 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.
    • 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.
  • 48
    • 34247843445 scopus 로고    scopus 로고
    • 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
    • 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.
  • 49
    • 34247865282 scopus 로고    scopus 로고
    • 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.
  • 50
    • 34247896109 scopus 로고    scopus 로고
    • 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.
  • 51
    • 34247896110 scopus 로고    scopus 로고
    • 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
    • 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.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.