화학공학소재연구정보센터
Journal of Polymer Science Part B: Polymer Physics, Vol.38, No.8, 1024-1036, 2000
Tube dilation process in star-branched cis-polyisoprenes
In current tube models for entanglement, the tube representing the topological constraint is considered to move with time. This tube motion results in the constraint release (CR) as well as the dynamic tube dilation (DTD), and an importance of DTD has been argued for entangled star chains. Under these backgrounds, this article examines the validity of the DTD molecular picture for the star chains. For monodisperse star chains having noninverted type-A (parallel) dipoles in respective arms, the normalized viscoelastic and dielectric relaxation functions mu(t) and Phi(t) were found to obey a relationship mu(t) congruent to [Phi(t)](2) if the tube actually dilates in the time scale of the star relaxation. For 6-arm star cis-polyisoprene (PI) chains (having those type-A dipoles), dielectric and viscoelastic measurements were conducted to test this DTD relationship. Both viscoelastic and dielectric properties exhibited characteristic behavior expected from DTD models (assuming the arm retraction in the dilating tube, the exponential increase of the relaxation time and broadening of the relaxation mode distribution with increasing arm molecular weight M-a. However, in the range of M-a, examined, M-a less than or equal to 8M(e) (M-e = entanglement spacing), the above DTD relationship was not valid for a dominant part of the slow relaxation land the models failed in this sense). Thus, for star chains at least in this range of M-a, the simple DTD picture assuming very rapid CR motion (rapid equilibration in the dilated tube) did not explain the slow relaxation behavior of star chains. This result in turn suggested the importance of the CR motion in this behavior.