Montmorillonite intercalation

Moleculady mixed composites of montmorillonite clay and polyimide which have a higher resistance to gas permeation and a lower coefficient of thermal expansion than ordinary polyimides have been produced (60). These polyimide hybrids were synthesized using montmorillonite intercalated with the ammonium salt of dodecylamine. When polymerized in the presence of dimethyl acetamide and polyamic acid, the resulting dispersion was cast onto glass plates and cured. The cured films were as transparent as polyimide. 

Y. Kojima, A. Usuki, M. Kawasumi, A. Okada, T. Kurauchi, 0. Kamigaito, Synthesis of nylon 6-clay hybrid by montmorillonite intercalated with e-caprolactam, Journal of Polymer Science Part A Polymer Chemistry, vol. 31, pp. 983-986,1993. 

Transition metal carbonyl clusters intercalated with lamellar materials such as graphite or smectites have been prepared and have been shown to be useful in catalysis 68). For instance, sodium montmorillonite was impregnated with [Ru(NH3)5]Cl3 in water under reflux. After flltration and drying, the resulting complex was dissolved in methanol and reduced with carbon monoxide at 80°C, 100 bar, for 16 hours. Infrared analysis has shown the formation of a sodium montmorillonite-intercalated [Ru3(CO),2] complex. This system was claimed to be active for the hydro-formylation of propene either with CO/Hj or CO/HjO in the presence of a basic promoter. 

For example, vinyl monomer-montmorillonite intercalate (VM-MMT), able to swell and disperse in organic solvents, was prepared by exchanging the mineral cations of MMT by vinylbenzyltrimethylammonium chloride. The resulting VM-MMT material rendered the mineral organophilic and having polymerizable moieties directly bonded to the lamellar surface of the mineral. Radical polymerization of S between the interlayers of 5,10,25, and 50 wt % of VM-MMT... 

Capkov, P., R.A.J. Driessen, M. Numan, H. Schenk, Z. Weiss, and Z. Klika. 1998a. Molecular simulations of montmorillonite intercalated with aluminum complex cations. Part I. Intercalation with [A1]304(0H)24+X(H20)]2 X](7 x)+. Clay Clay Miner. 46 232-239. 

The Eq. (55) was received for nanocomposites polymer/organoclay with oiganoclay intercalated structure and its application in the given case proves to be correct by organoclay packets (tactoids) (N > ) availability, that is a typical sign of Na -montmorillonite intercalated stmcture [56]. For nanocomposites PBT/MMT value is varied within the limits of 1.5-16.6 within the range of W=l lO mass. % [70]. 

Kojima Y., Usuki A., Kawasumi M., Okada A., Kurauchi T., Kamigaito 0.,(1993). "Synthesis of nylon 6-clay hybrid by montmorillonite intercalated with 3- caprolactam". Journal of Polymer Science. Part A, Vol.31, p. 983. 

Bora, M. Ganguli, J. N. Dutta, D. K (2000). Thermal and spectroscopic studies on the decomposition of [Ni di(2-aminoethyl)amine 2]- and [Ni(2,2" 6",2"-terpyridine)2]-Montmorillonite intercalated composites Thermochimica Acta. Vol. 346, p.169-175. Ghang, M. Y. Juang, R. S. (2004). Adsorption of tannic acid, humic acid and dyes from water using the composite of chitosan and activated clay. Journal of Colloid and Interface Science. Vol. 278, pp.18-25. 

Pospisil, M., Capkova, R, Merinska, D., Malac, Z., and Simonik, J. 2001. Structure analysis of montmorillonite intercalated with cetylpyridinium and cetyltrimethylammonium Molecular simulations and XRD analysis. Journal of Colloid Interface and Science 236 127-131. 

Kuppa, V. and Manias, E. 2002. Computer simulation of PEO/layered silicate nanocomposites 2. Lithium dynamics in PEO/Li montmorillonite intercalates. 

Fig. 3. Evolution of the d-spacing showing montmorillonite intercalation in PP-MA oligomer (I), and no subsequent change upon further blending with PP (II). Reproduced from Ref 9.

FIGURE 15 Proposed microstructures of the Ci2AzoC5N -montmorillonite intercalation compound. 

FIGURE 4 Cross-sectional view of Na montmorillonite intercalated with a monolayer of imogolite (SiAl203(0H)4). (From Ref. 5.)... 

F. Avalos, J. C. Ortiz, R. Zitzumbo, M. A. Lopez-Manchado, R. Verdejo, and M. Arroyo, Effect of montmorillonite intercalant structure on the cure parameters of natural rubber. European Polymer Journal, 44 (2008), 3108-15. 

Ogawa M, Ishikawa A (1998) Controlled microstructures of amphiphilic cationic azobenzene-montmorillonite intercalation compounds. J Mater Chem 8(2) 463 67... 

Kojima, Y. Usuki, A. Kawasumi, M. Okada, A. Kurauchi, T. Kamigaito, O. Synthesis of polyamide 6-clay hybrid by montmorillonite intercalated with e-caprolactam. J. Polym. Sci. Polym. Chem. 1993, 34(4), 983-986. 

As discussed in the previous chapter concerning the structure of smectite clays, it was pointed out that these clays are turbostatic and have WAX patterns that only exhibit 001 or hkO reflections with no hkl reflections. The hkO reflections are invariant and can be used to confirm the presence of the clay in a composite at any level of exfoliation. The 001 reflections are a result of the basal spacing between the clay plates as stacks in tactoids. These peaks are highly variable and are dependent upon a number of variables, including level of exfoliation, intercalate type, and level of order. Figure 3.1 illustrates these two types of reflection for montmorillonite intercalated with dodecylpyrrolidone surface treatment where the peak at approximately 20° two theta is of the hkO type and the peaks at 2.58, 5.26, and 7.84 are of the 001 type. The three peaks are related, being the 001, 002, and 003 reflections. 

Figure 3.1 X-ray diffraction pattern of montmorillonite intercalated with dodecylpyrrolidone.

Liu H, Zhang W, Zheng S. Montmorillonite intercalated by ammonium of octaaminopropyl polyhedral oligomeric silsesquioxane and its nanocomposites with epoxy resin. Polymer 2005 46 157-65. 

Figure 1.3 Organically modified montmorillonite intercalation with caprolactam. Reproduced from reference 36 with permission from Elsevier.

Optically transparent nanocomposites were prepared via twin-screw extrusion of a medical-grade flexible PVC resin and an organically modified montmorillonite. Intercalation and orientation of the montmorillonite layers were observed via x-ray diflfaction. A positive influence on barrier properties was noted, ineluding a five-fold increase in oxygen barrier at minimal clay loading. Consistent with the literature, no significant changes in thermal stability in air were observed. 

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