Liquid-Crystal Ordering and Microphase Separation in the Lamellar Phase of Rod-Coil-Rod Triblock Copolymers. Molecular Theory and Computer Simulations

A molecular model of the orientationally ordered lamellar phase exhibited by asymmetric rod-coil-rod triblock copolymers has been developed using the density-functional approach and generalizing the molecular-statistical theory of rod-coil diblock copolymers. An approximate expression for the free energy of the lamellar phase has been obtained in terms of the direct correlation functions of the system, the Flory-Huggins parameter and the Maier-Saupe orientational interaction potential between rods. A detailed derivation of several rod-rod and rod-coil density-density correlation functions required to evaluate the free energy is presented. The orientational and translational order parameters of rod and coil segments depending on the temperature and triblock asymmetry have been calculated numerically by direct minimization of the free energy. Different structure and ordering of the lamellar phase at high and low values of the triblock asymmetry is revealed and analyzed in detail. Asymmetric rod-coil-rod triblock copolymers have been simulated using the method of dissipative particle dynamics in the broad range of the Flory-Huggins parameter and for several values of the triblock asymmetry. It has been found that the lamellar phase appears to be the most stable one at strong segregation. The density distribution of the coil segments and the segments of the two different rods have been determined for different values of the segregation strength. The simulations confirm the existence of a weakly ordered lamellar phase predicted by the density-functional theory, in which the short rods separate from the long ones and are characterized by weak positional ordering.

Different Mechanisms of Translational Symmetry Breaking in Liquid-Crystal Coil–Rod–Coil Triblock Copolymers

A molecular-statistical theory of coil–rod–coil triblock copolymers with orientationally ordered rod-like fragments has been developed using the density functional approach. An explicit expression for the free energy has been obtained in terms of the direct correlation functions of the reference disordered phase, the Flory–Huggins parameter and the potential of anisotropic interaction between rigid rods. The theory has been used to derive several phase diagrams and to calculate numerically orientational and translational order parameter profiles for different polymer architecture as a function of the Flory–Huggins parameter, which specifies the short-range repulsion and as functions of temperature. In triblock copolymers, the nematic–lamellar transition is accompanied by the translational symmetry breaking, which can be caused by two different microscopic mechanisms. The first mechanism resembles a low dimensional crystallization and is typical for conventional smectic liquid crystals. The second mechanism is related to the repulsion between rod and coil segments and is typical for block copolymers. Both mechanisms are analyzed in detail as well as the effects of temperature, coil fraction and the triblock asymmetry on the transition into the lamellar phase.

Compatibility study of plasticizing additives based on recycled raw materials in the petrochemical with elastomer matrix

The compatibility of SRI-3 polyisoprene rubber with plasticizing additives based on recycled petrochemical raw materials (DVCH, DVCH with modifying additive (MA) in the amount of 0.5; 1.0; 2.5; 5.0 and 10.0% mas.) in comparison with industrial petroleum oils (PO-6 and I-20). The compatibility of polymer with a plasticizer additive was evaluated by of experimental data using the equilibrium swelling method. As a result, the polimer-plasticizer interaction parameter (Huggins parameter) and the diffusion coefficient of plasticizing components in the polymer volume were determined. Analysis of the experimental data showed that the plasticizer component based on recycled petrochemical raw materials DVCH has better compatibility with the elastomer matrix SRI-3 compared to industrial oils PO-6 and I-20. Was established that the use of modifying additives in the amount of 0.5 and 1.0% mas. leads to an increase in the diffusion coefficient and a decrease in the Huggins parameter in comparison with DVCH in individual form It indicates their better compatibility with rubber SRI-3. Was shown that a further increase in the content of modifying additive (more than 1.0% mas.) in the volume of plasticizing component DVCH is impractical. This leads to a deterioration of the parameters, and, as a result, to a worse compatibility with the elastomer.

Molecular Dynamic and Mesoscopic Dynamic Simulations for Polymer Blends

The compatibilities of polymer blends, Polypropylene (PP) and Polyamide12(PA12) with the quantity ratio 10/90, was simulated by Molecular Dynamics (MD) and Mesoscopic Dynamic simulation (MesoDyn) simulations. Cohesive energy density (CED) and solubility parameters (δ) of pure substances and PP/PA12 blends were got by MD simulations. Flory-Huggins parameter was calculated based on CED values. The mesoscale simulation was related to the molecular simulation through Flory-Huggins parameter. Free energy density and the density profiles were got through MesoDyn simulation. Results showed that solubility parameter difference (Δδ) of PP/PA12 is 4.092 and free energy density value is 0.17 in the equivalent system. And phase separation behavior was observed in the density profiles. All these indicates that PP and PA12 is not miscible which is the same as the experiment results.