Organoclays

Organoclays are the most widely used inorganic thickeners in the paint and coating industry. They are derived by modification of naturally occurring laminar silicates (clays) such as hectorite and bentonite. They have replaceable cations (Na Ca or Lk) on the surface of the crystal that are replaced, through an ion exchange reaction, by organic quaternary ammonium cations such as [dimethyldioctadecylammo-nium] or [dimethylbenzyloctadecylammonium]. Occasionally a blend of quaternary amines is used to tailor the properties of the product. 

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Another significant use for dialkyl dimethyl quaternary ammonium salts and alkylhenzyl dimethyl ammonium salts is in preparing organoclays for use as drilling muds, paint thickeners, and lubricants. 

The single largest market for quaternary ammonium compounds is as fabric softeners. In 1993 this market accounted for over 50,000 metric tons of quaternaries in the United States (235). Consumption of these products is increasing at an annual rate of about 2—3%. The hair care market consumed over 9000 metric tons of quaternary ammonium compounds in 1992 (236). The annual consumption for organoclays is estimated at 12,700 metric tons (237). Esterquats have begun to gain market share in Western Europe and growth is expected to continue. 

The main use of these clays is to control, or adjust, viscosity in nonaqueous systems. Organoclays can be dispersed in nonaqueous fluids to modify the viscosity of the fluid so that the fluid exhibits non-Newtonian thixotropic behavior. Important segments of this area are drilling fluids, greases (79,80), lubricants, and oil-based paints. The most used commercial products in this area are dimethyl di (hydrogen a ted tallow) alkylammonium chloride [61789-80-8] dimethyl (hydrogen a ted tallow)aLkylbenzylammonium chloride [61789-72-8] and methyldi(hydrogenated tallow)aLkylbenzylammonium chloride [68391-01-5]. 

Ogata et al. (1997) first prepared PLA/ organoclay (OMMT) blends by dissolving the polymer in hot chloroform in the presence of dimethyl distearyl ammonium modified MMT (2Ci8MMT). XRD results show that the silicate layers forming the day could not be intercalated in the PLA/MMT blends, prepared by the solvent-cast method. Thus, the clay existed in the form of tactoids, consisting several stacked silicate monolayers. 

In the matrix of PLA/ polycaprilactone (PCL)/OMMT nano-composites, the silicate layers of the organoclay were intercalated and randomly distributed (Zhenyang et at, 2007). The PLA/PCL blend significantly improved the tensile and other mechanical properties by addition of OMMT. Thermal stability of PLA/PCL blends was also explicitly improved when the OMMT content is less than 5%wt. Preparation of PLA/thermoplastic starch/MMT nano-composites have been investigated and the products have been characterized using X-Ray diffraction, transmission electron microscopy and tensile measurements. The results show improvement in the tensile and modulus, and reduction in fracture toughness (Arroyo et ah, 2010). 

FACTORS AFFECTING THE TYPE OF ORGANOCLAY HYBRID FORMED... 

Many different polymers have already been used to synthesize polymer-clay nanocomposites. In this section, an overview of the advances that have been made during the last 10 years in the intercalation and the delamination of organoclay in different polymeric media is given. The discussion mainly covers the work involving thermoset nanocomposites along with a brief discussion about thermoplastic-based nanocomposites. 

Literature search shows that epoxy-based nanocomposites have been prepared by many researchers [34-38]. Becker et al. have prepared nanocomposites based on various high-functionahty epoxies. The mechanical, thermal, and morphological properties were also investigated thoroughly [39 3]. The cure characteristics, effects of various compatibilizers, thermodynamic properties, and preparation methods [16,17,44 9] have also been reported. ENR contains a reactive epoxy group. ENR-organoclay nanocomposites were investigated by Teh et al. [50-52]. 

Recently a lot of attention is being given to the field of latex-based nanocomposites. Various organoclays as well as pristine clays have been intercalated in aqueous medium with NR latex, SBR latex, NBR latex, as well as carboxylated nitrile mbber (XNBR) latex [184—187], to achieve a good degree of dispersion. 

The researchers also studied that the addition of organoclay into the NR increases the stiffness remarkably (Figure 28.16). It has been studied that the effect of organoclay is not significant below the glass transition temperature (Figure 28.17) [28]. 

FIGURE 28.16 Storage modulus vs temperature of organoclay-loaded rubber nanocomposite. (From Teh, P.L. et al., J. Appl. Polym. Sci., 100, 1083, 2006.)... 

The exchange of inorganic cations by organic surfactant ions in the clay galleries not only makes the organoclay surface compatible with monomer or polymer matrix, but also de-... 

Rubber-clay nanocomposites are particularly attractive for potential applications where enhanced barrier properties are desired. Organoclays for rubber intercalation were prepared... 

Polyimide-clay nanocomposites constitute another example of the synthesis of nanocomposite from polymer solution [70-76]. Polyimide-clay nanocomposite films were produced via polymerization of 4,4 -diaminodiphenyl ether and pyromellitic dianhydride in dimethylacetamide (DMAC) solvent, followed by mixing of the poly(amic acid) solution with organoclay dispersed in DMAC. Synthetic mica and MMT produced primarily exfoliated nanocomposites, while saponite and hectorite led to only monolayer intercalation in the clay galleries [71]. Dramatic improvements in barrier properties, thermal stability, and modulus were observed for these nanocomposites. Polyimide-clay nanocomposites containing only a small fraction of clay exhibited a several-fold reduction in the... 

Poly(styrene-fc-butadiene) copolymer-clay nanocomposites were prepared from dioctadecyldimethyl ammonium-exchanged MMT via direct melt intercalation [91]. While the identical mixing of copolymer with pristine montmorillonite showed no intercalation, the organoclay expanded from 41 to 46 A, indicating a monolayer intercalation. The nanocomposites showed an increase in storage modulus with increasing loading. In addition, the Tg for the polystyrene block domain increased with clay content, whereas the polybutadiene block Tg remained nearly constant. 

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