Rheological Behavior for Polymer Melts and Concentrated Solutions——Part Ⅶ: A Quantitative Verification for the Molecular Theory of Non-linear Viscoelasticity with Entanglement Constraints in Polymer Melts

Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) over dot), psi (10)((gamma) over dot) and shear rate ((gamma) over dot), and topologically constrained dimension number n ' and a were derived. Linear viscoelastic parameters (eta (0) and G(N)(0)) and topologically constrained dimension number (n ' a and <(<upsilon>)over bar>) as a function of the primary molecular weight (M-n), molecular weight between entanglements (M-C) and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters (eta (0), psi (10), G(N)(0) and J(e)(0)), topologically constrained dimension number (n ', a and v) and molecular weight (M-n, M-c and M-e) from the shear flow measurements was proposed. It was used to determine those parameters and structures of HDPE, making a good agreement between these values and those obtained by other methods. The agreement affords a quantitative verification for the molecular theory of nonlinear viscoelasticity with constrained entanglement in polymer melts.

Enhancing Molecular Chain Entanglement and π-π Stacking Toward the Improvement of Shape Memory Performance of Polyimide

Thermoplastic polyimides(PIs)with shape memory potential have received growing attention in recent years.In this work,highperformance thermoplastic PIs were fabricated by introducing PIs with chain rigidity(r-PI)into PI with chain flexibility(f-PI).The influences of molecular chain entanglement andπ-πinteractions on their thermomechanical and shape memory properties were investigated.The degree of molecular chain entanglement was quantitively characterized based on dynamic mechanical analysis(DMA).Theπ-πinteractions were investigated in detail by X-ray diffraction(XRD)and UV-Vis spectroscopy.It was found that the entanglement density increased andπ-πinteractions became stronger with the introduction of r-PI into f-PI,leading to the improvement of shape recovery.Moreover,a broad and increased glass transition temperature(T_(g))was achieved,endowing the PIs with multiple shape memory properties.The synergistic effects of increased entanglement density and enhancedπ-πinteractions were beneficial to regulating interchain interactions and thereby achieving high shape memory performance of the PIs.

Dynamics of Poly(methyl methacrylate)in Ionic Liquids with Different Concentration and Cationic Structures

The dynamic behavior of entangled poly(methyl methacrylate)(PMMA)chains in both the traditional monocationic ionic liquid(MIL)and synthetic dicationic ionic liquid(DIL)with the same anion bis[(trifluoromethyl)sulfonyl]imide([TFSI]−)has been examined over the wide composition range using differential scanning calorimetry and rheological measurements.PMMA/DIL and PMMA/MIL systems exhibit two glass transitions in the midrange of composition due to self-concentration effects.PMMA in DIL shows slower relaxation behavior,however,after the iso-free-volume correction,the terminal relaxation timeτ_(0)of PMMA in both the DIL and MIL presents the power law behaviorτ_(0)∼ϕ^(v)with exponent v conforming to experimental results for conventional polymer solutions(v=2.0±0.2).At high ILs concentration(70%),the entanglement molecular weight M_(e)of PMMA/DIL system is lower than that of PMMA/MIL system owing to the formation of additional physical network in DIL,while the difference of M_(e)is reversed at low ILs content.The composition dependence might be related to the fact that the probability of formation of physical cross-linking points in linked double imidazolium ring increases with the increase of DIL content.The recovered creep strain of PMMA/DIL is almost 18 times of PMMA/MIL,exhibiting significantly better viscoelastic behavior.