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Influence of Network Structure on Glass Transition Temperature of Elastomers.

ABSTRACT: It is generally believed that only intermolecular, elastically-effective crosslinks influence elastomer properties. The role of the intramolecular modifications of the polymer chains is marginalized. The aim of our study was the characterization of the structural parameters of cured elastomers, and determination of their influence on the behavior of the polymer network. For this purpose, styrene-butadiene rubbers (SBR), cured with various curatives, such as DCP, TMTD, TBzTD, Vulcuren®, DPG/S₈, CBS/S₈, MBTS/S₈ and ZDT/S₈, were investigated. In every series of samples a broad range of crosslink density was obtained, in addition to diverse crosslink structures, as determined by equilibrium swelling and thiol-amine analysis. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to study the glass transition process, and positron annihilation lifetime spectroscopy (PALS) to investigate the size of the free volumes. For all samples, the values of the glass transition temperature (Tg) increased with a rise in crosslink density. At the same time, the free volume size proportionally decreased. The changes in Tg and free volume size show significant differences between the series crosslinked with various curatives. These variations are explained on the basis of the curatives' structure effect. Furthermore, basic structure-property relationships are provided. They enable the prediction of the effect of curatives on the structural parameters of the network, and some of the resulting properties. It is proved that the applied techniques-DSC, DMA, and PALS-can serve to provide information about the modifications to the polymer chains. Moreover, on the basis of the obtained results and considering the diversified curatives available nowadays, the usability of "part per hundred rubber" (phr) unit is questioned.

SUBMITTER: Bandzierz K

PROVIDER: S-EPMC5456841 | biostudies-other | 2016 Jul

REPOSITORIES: biostudies-other

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Project description:Intermolecular interactions between the constituents of a polymer nanocomposite at the polymer-particle interface strongly affect the segmental mobility of polymer chains, correlated with their glass transition behavior, and are responsible for the improved dynamical viscoelastic properties. In this work, we emphasized on the evolution of characteristic interfaces and their dynamics in silica (SiO2 NP)-reinforced, solution-polymerized, styrene butadiene rubber (SSBR) composites, whose relative prevalence varied with the phosphonium ionic liquid (PIL) volume fraction, used as an interfacial modifier. The molecular origins of such interfaces were examined through systematic dielectric spectroscopy, molecular dynamics (MD) simulations, and dynamic-mechanical analyses. The PIL facilitated H-bonding, cation-π, surface-phenyl, and van der Waals interfacial interactions between SSBR and SiO2 NP, thereby regulating the polymer chain dynamics, orientation, and mean-square displacement. Specifically, the mass density profiles from MD simulations revealed the dynamic gradient of polymer chains in the interfacial region as a function of radial distance from the center of mass of the SiO2 NP surface. The results showed a structuring effect to result in well-resolved density peaks at specific radial distances with the tangential orientation of styrene monomers in the vicinity of the SiO2 NP surface. These domino effects highlighted strong interfacial interactions to have an indispensable effect on the viscoelastic performance and thermal motion of SSBR molecular chains, leading to a higher glass transition temperature (T g) by ∼15 K, validating the experimental data. More importantly, our results gave new insights into the fundamental understanding of the fact that the strength of intermolecular interactions induced by PIL at the polymer-particle interface is the key to control the α-relaxation dynamics and T g optimization, desired for specific applications.

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Influence of Network Structure on Glass Transition Temperature of Elastomers.

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