Title

Melt-intercalation studies of polystyrene ionomers in pristine montmorillonite

Date of Completion

January 2006

Keywords

Chemistry, Polymer|Engineering, Materials Science

Degree

Ph.D.

Abstract

The main objective of this study was to examine the use of ionomers, specifically alkylamine-neutralized sulfonated polystyrene (SPS) for promoting intercalation into unmodified sodium montmorillonite clay and its use as a compatabilizer for intercalating another polymer into unmodified silicate clay. The processing parameters and chemical structure of polymers which led to the formation of partially intercalated/exfoliated morphologies were investigated. ^ Melt-intercalated polymer layered silicate nanocomposites (PLSNs) are made by mixing polymers and organically modified silicates by the application of shear forces. However, the thermal decomposition temperatures of the organic modifications are usually comparable to the processing temperatures of most of the polymers. Hence, in this work modification of the polymer, rather than the clay, for promoting melt intercalation, specifically the introduction of alkyl ammonium salt groups along the polymer chain was considered. ^ In this study the effects of viscosity, shear rates and mixing times on the morphology of nanocomposites were investigated. The effect of ionic content in the polymer chain of SPS in the batch mixtures of SPS and PS was researched. We also compared the effect on the extent of intercalation in these silicate clay galleries as a function of size of the counter-ions by varying the alkyl chain length and as a function of basicity of these counter-ions by varying the number of alkyl substituents that are attached on the N of the amine. ^ The melt mixing of pristine Na-Mmt with alkyl ammonium and quaternary ammonium salts of SPS ionomers, resulted in an increase in the silicate gallery spacing consistent with intercalation. Mixtures of the ionomer with PS exhibited similar gallery spacing increases, indicating that the ionomer is an effective compatibilizing agent for the melt-intercalation of hydrophobic polymers into the clay. The extent of intercalation was independent of the melt processing conditions employed in this study and also did not change as the molecular weight of ionomer was varied. Intercalation appeared to be dependent on the charge ratio between the ionomer and the clay. The increase in gallery spacing achieved was a function of size of the alkylamine counter-ions used. The nanocomposites containing ionomers exhibited higher storage moduli compared to nanocomposites without the compatibilizer.^

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