Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains
AuthorsShivokhin, Maksim E.
Read, Daniel J.
Likhtman, Alexei E.
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Polymer Synthesis Laboratory
Online Publication Date2017-05-30
Print Publication Date2017-06-13
Permanent link to this recordhttp://hdl.handle.net/10754/625597
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AbstractWe propose and verify methods based on the slip-spring (SSp) model [ Macromolecules 2005, 38, 14 ] for predicting the effect of any monodisperse, binary, or ternary environment of topological constraints on the relaxation of the end-to-end vector of a linear probe chain. For this purpose we first validate the ability of the model to consistently predict both the viscoelastic and dielectric response of monodisperse and binary mixtures of type A polymers, based on published experimental data. We also report the synthesis of new binary and ternary polybutadiene systems, the measurement of their linear viscoelastic response, and the prediction of these data by the SSp model. We next clarify the relaxation mechanisms of probe chains in these constraint release (CR) environments by analyzing a set of "toy" SSp models with simplified constraint release rates, by examining fluctuations of the end-to-end vector. In our analysis, the longest relaxation time of the probe chain is determined by a competition between the longest relaxation times of the effective CR motions of the fat and thin tubes and the motion of the chain itself in the thin tube. This picture is tested by the analysis of four model systems designed to separate and estimate every single contribution involved in the relaxation of the probe's end-to-end vector in polydisperse systems. We follow the CR picture of Viovy et al. [ Macromolecules 1991, 24, 3587 ] and refine the effective chain friction in the thin and fat tubes based on Read et al. [ J. Rheol. 2012, 56, 823 ]. The derived analytical equations form a basis for generalizing the proposed methodology to polydisperse mixtures of linear and branched polymers. The consistency between the SSp model and tube model predictions is a strong indicator of the compatibility between these two distinct mesoscopic frameworks.
CitationShivokhin ME, Read DJ, Kouloumasis D, Kocen R, Zhuge F, et al. (2017) Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains. Macromolecules 50: 4501–4523. Available: http://dx.doi.org/10.1021/acs.macromol.6b01947.
SponsorsWe thank Dietmar Auhl and Hiroshi Watanabe for kindly supplying experimental data of
PublisherAmerican Chemical Society (ACS)