Yuqiang Qian

Synthesis and Properties of Vermiculite-Reinforced Polyurethane Nanocomposites

Natural vermiculite was modified by cation exchange with long-chain quaternary alkylammonium salts and then dispersed in polyether-based polyols with different structures and ethylene oxide/propylene oxide ratios. The dispersions were evaluated by X-ray scattering and rheology. In all polyol dispersions tested, polyols were intercalated into the vermiculite interlayers. Also, significant shear thinning behavior was observed. A large interlayer spacing of ∼90 Å was achieved in one polyol suitable for polyurethane elastomer synthesis. In polyurethane made with this polyol, clay platelets were extensively intercalated or exfoliated. The composites showed a >270% increase in tensile modulus, >60% increase in tensile strength, and a 30% reduction in N(2) permeability with a loading of 5.3 wt % clay in polyurethane. Differential scanning calorimetry and dynamic mechanical analysis revealed that the nanoclay interacts with the polyurethane hard segments.

Polyol-Assisted Vermiculite Dispersion in Polyurethane Nanocomposites

The largest use of polyurethane (PU) is as closed cell rigid foams for thermal insulation. One problem is loss of blowing gases, which leads to slow increase in thermal conductivity. PU composites with plate-like nanofillers create a diffusion barrier, reducing gas transport and slowing insulation aging. In this research, a new in situ intercalative polymerization is described to disperse vermiculite (VMT) in PU. When VMT was modified by cation exchange with long-chain quaternary ammonium, the dispersion in methylene diphenyl diisocyanate (MDI) was significantly improved. Dispersion of clay in MDI was further improved by combining high intensity dispersive mixing with a polyol-clay preblend (master-batch). The VMT dispersibility was characterized using rheology, microscopy, and X-ray scattering/diffraction. With the method of polyol-assisted VMT dispersion, electron microscopy revealed extensive intercalation and exfoliation of clay particles. In contrast, simple mixing of organoclay in MDI resulted in macroscopic localization and poor distribution of clay particles in PU. The final nanocomposites prepared by the master-batch method showed enhancement of mechanical properties (85% increase in elastic modulus) and reduction in permeability to CO2, as much as 40%, at a low clay concentration of 3.3 wt %.