Abstract
The crossover from linear to branched polymer dynamics in highly entangled melts was investigated with a series of asymmetric three-arm stars of poly(ethylene-alt-propylene). Two arms of equal length formed a linear backbone, kept constant through the series, while branches of various length were appended as the third arm. The materials were made by carbanionic polymerization of isoprene and the judicious application of chlorosilane linking chemistry. Subsequent saturation of the polymeric double bonds with deuterium and hydrogen, followed by fractionation, led to a set of structurally matched, nearly monodisperse pairs of deuterium-labeled and fully hydrogenous samples. Dynamic moduli were measured over wide ranges of frequency and temperature. With increasing branch length, the resulting master curves evolve smoothly, but with surprising rapidity, from the relatively narrow terminal spectrum of linear polymers to the much broader spectrum of symmetric stars. The viscosity ηo increases rapidly with branch length, and the diffusion coefficient D, obtained by forward recoil spectrometry, decreases even more rapidly. The product ηoD, however, distinguishes the transition from linear to branched polymer dynamics most clearly: for a backbone with about 38 entanglements, the crossover is already approaching completion for a single mid-backbone branch with only about three entanglements. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1943–1954, 1997
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
More From: Journal of Polymer Science Part B: Polymer Physics
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.