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Volumn 42, Issue 5, 2009, Pages 1739-1748

Combined SANS, SEC, NMR, and UV-Vis studies of simultaneous living anionic copolymerization process: simultaneous elucidation of propagating living chains at three different length scales

Author keywords

[No Author keywords available]

Indexed keywords

ANIONIC COPOLYMERIZATION; BLOCK-CHAIN; CHAIN-ENDS; CONVERSION RATES; COPOLYMERIZATION PROCESS; DIFFERENT LENGTH SCALE; DILUTE SOLUTION; HIGHER-ORDER STRUCTURE; LIVING POLYMERS; LOCAL STRUCTURE; POLYMERIZATION PROCESS; PRIMARY STRUCTURES; SMALL-ANGLE NEUTRON SCATTERING; STAR-LIKE; STRUCTURAL CHANGE; TIME CHANGE; TIME REGION; TIME RESOLVED MEASUREMENT; TIME-RESOLVED SANS; UV-VIS STUDIES;

EID: 66549102826     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma8017519     Document Type: Article
Times cited : (15)

References (40)
  • 4
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    • U.S. Patent 2975160
    • Zelinski, R. P. U.S. Patent 2975160, 1961.
    • (1961)
    • Zelinski, R.P.1
  • 7
    • 0003877321 scopus 로고
    • Burke, J. J, Weiss, V, Eds, Syracuse University Press: Syracuse, NY
    • Hsieh, H. L. In Block and Graft Copolymers Burke, J. J., Weiss, V., Eds.; Syracuse University Press: Syracuse, NY, 1973.
    • (1973) Block and Graft Copolymers
    • Hsieh, H.L.1
  • 12
    • 66549091684 scopus 로고    scopus 로고
    • Stellbrink, J.; Willner, L.; Richter, D.; Lindner, P.; Fetters, L. J.; Huang, J. S Macromolecules 1998, 31, 4189-4197. Macromolecules 1999, 32, 5321-5329.
    • Stellbrink, J.; Willner, L.; Richter, D.; Lindner, P.; Fetters, L. J.; Huang, J. S Macromolecules 1998, 31, 4189-4197. Macromolecules 1999, 32, 5321-5329.
  • 16
    • 66549115916 scopus 로고    scopus 로고
    • n,final will be found in eq 9 and ref 23.
    • n,final will be found in eq 9 and ref 23.
  • 17
    • 66549116673 scopus 로고    scopus 로고
    • Because some amount of initiators always become inactive due to the presence of impurities, in this study we calculated the effective initiator concentration and compared it with the fed initiator concentration in order to check if the polymerization process is well controlled or not. The effective initiator concentration is calculated as [Ini]eff, Wini/ Mn,final, 10.6 mM, where Wini represents the total weight of fed monomers (0.522 g) per total of the reaction system, V total, 90 × 10-6, 6.3 × 10-3, 0.38× 10-3, 0.29× 10-3)L, 7.06 × 10-3 L (74 g/L) before the polymerization, and Mn,final represents the total molecular weight after the polymerization and termination ∼7000, as will be detailed in ref 23. The theoretical initiator concentration, Ini]theor, can be calculated from the fed initiator amount as
    • ini is moles of the fed initiator (90 μL solution of 1.0 M sec-BuLi).
  • 23
    • 66549104193 scopus 로고    scopus 로고
    • From SEC, the apparent number averaged molecular weight of the copolymer chain, Mn,app, can be calculated directly on the basis of polystyrene standard calibration. However, we must take into account the size difference between I and S monomeric units in the copolymer to estimate true molecular weight Mn from Mn,app. For this purpose, we used a calibration factor 1.6 estimated for homoPI. This factor 1.6 was determined by measuring Mn,PI,app's by SEC with PS standard for a series of PI homopolymers having different Mn,PI's which were independently measured by a membrane osmometer. We assume that the factor 1.6 is applicable to the copolymer also. We further assume that the apparent number average molecular weight per copolymer chain at the end of polymerization, Mnfinal-app ∼9000, can be expressed as follows: M n,final,app, 1.6M NI,finanl, MsNs,final ∼9
    • s,final ∼7000 (III)
  • 26
    • 66549127725 scopus 로고    scopus 로고
    • Ph.D. Dissertation. Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University: Kyoto, Japan
    • Tanaka, H. Ph.D. Dissertation. Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University: Kyoto, Japan, 2008.
    • (2008)
    • Tanaka, H.1
  • 38
    • 66549088058 scopus 로고    scopus 로고
    • -] = 10.6 mM which is the same total anion concentration as the copolymerization reaction in this study.
    • -] = 10.6 mM which is the same total anion concentration as the copolymerization reaction in this study.


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