메뉴 건너뛰기




Volumn 35, Issue 21, 2002, Pages 8126-8138

Relationship between chain length and the concentration dependence of polymer and oligomer self-diffusion in solution

Author keywords

[No Author keywords available]

Indexed keywords

SELF-DIFFUSION PROCESSES;

EID: 0037044350     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma020859w     Document Type: Article
Times cited : (28)

References (94)
  • 4
    • 0344252790 scopus 로고
    • Although Rouse theory (Rouse, P.E. J. Chem. Phys. 1953, 21, 1273) was originally posed for bulk polymer systems, it has been employed extensively to describe behavior in polymer solutions.
    • (1953) J. Chem. Phys. , vol.21 , pp. 1273
    • Rouse, P.E.1
  • 5
    • 0010944286 scopus 로고    scopus 로고
    • note
    • Equivalently, the monomeric friction coefficient may be associated with a subunit on the chain consisting of a number of repeat units; the overall frictional drag is then a product of the monomeric friction coefficient and the number of subunits making up the chain.
  • 17
    • 0010944903 scopus 로고    scopus 로고
    • note
    • x,m rather than β. β is used here in order to emphasize the empirical origin of the value of the exponent.
  • 18
    • 0010941873 scopus 로고    scopus 로고
    • note
    • In the context of Vrentas-Duda free volume theory, β is interpreted to be the ratio of jumping unit size of the polymer to that of the solvent. However, the fundamental meaning associated with β may not be that straightforward.
  • 24
    • 0010893817 scopus 로고    scopus 로고
    • note
    • Concentrated solutions of glassy polymer such as PS and PMMA may require days to weeks at ambient conditions or elevated temperatures in order for solution homogeneity to be achieved. See refs 25-29 for examples of such systems.
  • 56
    • 0022513105 scopus 로고
    • Miltz, J. Polymer 1986, 27, 105.
    • (1986) Polymer , vol.27 , pp. 105
    • Miltz, J.1
  • 86
    • 0010902196 scopus 로고    scopus 로고
    • note
    • References 66 and 70 provide additional data for PS self-diffusion in PS/toluene solutions measured near 25 °C. However, these data were excluded from analysis here because of anomalies in the data or a lack of correspondence with PS self-diffusion in PS/toluene solutions measured by PFG-NMR methods in this study. For example, analysis of 10K PS, 35K PS, and 100K PS self-diffusion data in ref 70 indicates an unexpected, strong chain-length dependence of the β value, with β values of 3.4, 5.6, and 10.2 being needed to describe the concentration dependence of PS self-diffusion in the 10K, 35K, and 100K systems, respectively. These values are well in excess of the β values obtained in this study and from analysis of the concentration dependence of 125K PS self-diffusion data by Fleischer (ref 53). Additionally, it is not possible to rationalize on physical grounds the major increase in β values in going from the 10K PS system to the 35K PS system. Likewise, the data for 17.9K PS self-diffusion in ref 66 indicate a much stronger concentration dependence of diffusion (β value = 3.5) as compared with the experimentally measured data for 16.7K PS diffusion shown in Figure 3 (β = 2.6). Given the reproducibility of the 16.7K PS data obtained in this study, the data set in ref 66 was not included in the analysis here.
  • 89
    • 0010832558 scopus 로고    scopus 로고
    • Ph.D. Dissertation, Northwestern University
    • Wisnudel, M.B. Ph.D. Dissertation, Northwestern University, 1996.
    • (1996)
    • Wisnudel, M.B.1
  • 92
    • 0010833164 scopus 로고    scopus 로고
    • note
    • 16 in their study of the concentration dependence of PMMA self-diffusion. The current study indicates that the concentration dependence of PS self-diffusion may be slightly weaker in toluene solution relative to styrene solution, which means that β values for PMMA self-diffusion would still have good correspondence with β values for PS self-diffusion, albeit with the unentangled PMMA systems yielding slightly higher values. A second option would be to compare the β values for PMMA self-diffusion in its monomer, methyl methacrylate, to β values for PS self-diffusion in styrene. It is expected that such a comparison would yield results quite similar to those observed in Figure 12.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.