Citation: . A COMPARATIVE STUDY OF CHAIN DYNAMICS OF DI-AND TRI-BLOCK COPOLYMERS IN SEMIDILUTE SOLUTION IN A NON-SELECTIVE SOLVENT*[J]. Chinese Journal of Polymer Science, ;2004, 22(6): 589-598. shu

A COMPARATIVE STUDY OF CHAIN DYNAMICS OF DI-AND TRI-BLOCK COPOLYMERS IN SEMIDILUTE SOLUTION IN A NON-SELECTIVE SOLVENT*

Received Date: 8 May 2004
Revised Date: 28 June 2004

The chain dynamics of a pair of diblock poly(styrene-b-butadiene) (PS210-b-PB960) and triblock poly(styrene-b-butadiene-b-styrene) (PS200-b-PB1815-b-PS200) copolymers in both dilute and semidilute toluene solutions has been comparatively studied by dynamic laser light scattering. As expected, the mutual diffusion of individual chain changes into a fast cooperative diffusion of the chain segments (blobs) between two neighboring entanglement points for both the copolymers as the solution changes from dilute to semidilute. Further increases of the concentration lead to a second slow relaxation mode. For the triblock chains, there exists an additional middle relaxation between the fast and the slow modes.The concentration (c) dependent study of the average characteristic decay time of the fast mode (f) reveals that 1/f ～ c-with 0.33 0.44, much smaller than 0.75 predicted or 0.72 observed for linear homopolymer chains in good solvent. It implies that the solvent quality of toluene for PB might not be as good as that for PS. Due to such a difference in solubility, it is reasonable to speculate that the PB and PS blocks are transiently segregated in semidilute solution. The relaxation of these transient PB and PS richer domains leads to the observed slow relaxation. Such a speculation is supported by the appearance of an additional slow relaxation mode in the study of polyisoprene-b-polystyrene-b-polyisoprene in semidilute solution in cyclohexane, a non-selective solvent, in which we alternated the solubility difference by a variation of the solution temperature.
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