TY - JOUR

T1 - Kinetics of chain collapse in dilute polymer solutions

T2 - Molecular weight and solvent dependences

AU - Maki, Yasuyuki

AU - Dobashi, Toshiaki

AU - Nakata, Mitsuo

N1 - Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.

PY - 2007

Y1 - 2007

N2 - The molecular weight and solvent dependences of the characteristic time of chain collapse were studied for poly(methyl methacrylate) (PMMA) of the molecular weight Mw =6.4× 106 and 1.14× 107 in pure acetonitrile (AcN) and in the mixed solvent of AcN+water (10 vol %). The size of PMMA chains was measured as a function of the time after the quench by static light scattering and the chain collapse processes were expressed by the plot of the expansion factor α2 vs ln t. The chain collapse in the mixed solvent AcN+water (10 vol %) was found to occur much faster than that in pure AcN, though the measurement of the former collapse process required several hours. In order to make a comparison between the rates of chain collapses, the fast chain collapse process was superposed on the slow one by scaling the time of the fast process as γt. The scale factor γ was determined by comparing the chain collapse processes of nearly the same equilibrium expansion factor with each other. Accordingly, the superposition of the collapse for Mw =6.4× 106 on that for Mw =1.14× 107 yielded γm =4.0±0.6 for the process in AcN+water and 5.5±0.6 in AcN. The superposition of the chain collapse process in AcN+water on that in AcN yielded γs =9.5±1.4 for Mw =6.4× 106 and 12.0±1.8 for Mw =1.14× 107. This analysis suggests that γm and γs are constant independent of each other. Thus, by assuming the molecular weight dependence of γm ∼ Mz, the characteristic time τexp of chain collapse was conjectured as τexp ∼κ Mz, where κ reflects the nature of solvent species. The ratio of κ for PMMA in AcN to that in AcN+water is given by γs. The exponent was estimated to be z=2.4±0.7 for AcN+water and 3.0±0.7 for AcN. These values are compatible with the theoretical prediction z=3 based on a phenomenological model, though the observed characteristic times are longer by several orders of magnitude than those of the theoretical prediction.

AB - The molecular weight and solvent dependences of the characteristic time of chain collapse were studied for poly(methyl methacrylate) (PMMA) of the molecular weight Mw =6.4× 106 and 1.14× 107 in pure acetonitrile (AcN) and in the mixed solvent of AcN+water (10 vol %). The size of PMMA chains was measured as a function of the time after the quench by static light scattering and the chain collapse processes were expressed by the plot of the expansion factor α2 vs ln t. The chain collapse in the mixed solvent AcN+water (10 vol %) was found to occur much faster than that in pure AcN, though the measurement of the former collapse process required several hours. In order to make a comparison between the rates of chain collapses, the fast chain collapse process was superposed on the slow one by scaling the time of the fast process as γt. The scale factor γ was determined by comparing the chain collapse processes of nearly the same equilibrium expansion factor with each other. Accordingly, the superposition of the collapse for Mw =6.4× 106 on that for Mw =1.14× 107 yielded γm =4.0±0.6 for the process in AcN+water and 5.5±0.6 in AcN. The superposition of the chain collapse process in AcN+water on that in AcN yielded γs =9.5±1.4 for Mw =6.4× 106 and 12.0±1.8 for Mw =1.14× 107. This analysis suggests that γm and γs are constant independent of each other. Thus, by assuming the molecular weight dependence of γm ∼ Mz, the characteristic time τexp of chain collapse was conjectured as τexp ∼κ Mz, where κ reflects the nature of solvent species. The ratio of κ for PMMA in AcN to that in AcN+water is given by γs. The exponent was estimated to be z=2.4±0.7 for AcN+water and 3.0±0.7 for AcN. These values are compatible with the theoretical prediction z=3 based on a phenomenological model, though the observed characteristic times are longer by several orders of magnitude than those of the theoretical prediction.

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U2 - 10.1063/1.2715596

DO - 10.1063/1.2715596

M3 - Article

C2 - 17430061

AN - SCOPUS:34047248882

VL - 126

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 13

M1 - 134901

ER -