Clay, montmorillonite

There are two major steps involved in clay particle dispersion in polymers to prepare nanocomposites intercalation and exfoliation, the latter sometimes 

Intercalation and exfoliation arise because of rubber elasticity entropic forces (84). When the intercalated monomers polymerize, or the preformed polymers diffuse into the clay galleries, they initially tend to be oriented parallel to the planar silicate layers. As described in Chapter 9, this mimics a type of biaxial stretching in a state of low entropy. As the chains coil up to increase their entropy, the silicate layers are forced further apart. 

The polyamide-6-montmoriUonite system was the first to be explored (79-81). As described above, the sodium ion in the clay was replaced by 12-aminododecanoic acid. This alone produces a type of intercalation, the size of the 12-aminododecanoic acid slightly forcing the silicate layers apart. The addition of e-caprolactam further forces the silicate layers apart. These effects are summarized in Table 13.7 (79). Note that the increasing length of the -amino 

Rgure 13.29 Schematic illusttations of the structures of (a) conventional, (b) intercalated, and (c) exfoliated polymer clay nanocomposites. Note that the clay interlayer spacing is fixed in intercalated materials, but larger and variable in the exfoliated materials. 

Of course, e-caprolactam is the monomer for polyamide-6.The ring-opening polymerization, in this case catalyzed by the carboxyl end groups on the 12-aminododecanoic acid, may be illustrated as follows  

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Nitrile Rubber. Vulcanized mbber sheets of NBR and montmorillonite clay intercalated with Hycar ATBN, a butadiene acrylonitrile copolymer have been synthesized (36). These mbber hybrids show enhanced reinforcement (up to four times as large) relative to both carbon black-reinforced and pure NBR. Additionally, these hybrids are more easily processed than carbon black-filled mbbers. 

Nylon-6. Nylon-6—clay nanometer composites using montmorillonite clay intercalated with 12-aminolauric acid have been produced (37,38). When mixed with S-caprolactam and polymerized at 100°C for 30 min, a nylon clay—hybrid (NCH) was produced. Transmission electron microscopy (tern) and x-ray diffraction of the NCH confirm both the intercalation and molecular level of mixing between the two phases. The benefits of such materials over ordinary nylon-6 or nonmolecularly mixed, clay-reinforced nylon-6 include increased heat distortion temperature, elastic modulus, tensile strength, and dynamic elastic modulus throughout the —150 to 250°C temperature range. 

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. 

Fig. 6. Pilot-scale kiln results for a fill fraction of 0.08% at 0.5 rpm and an initial toluene loading, on a dry, calcined, montmorillonite clay adsorbent, of 0.25 wt %, at A, 790°C B, 330°C and C, 190°C. The soHd lines are model fits using equation 24. The model simultaneously fits to all of the data (24).

Dehydration of 1-pentanol or 2-pentanol to the corresponding olefins has been accompHshed, in high purity and yields, by vapor-phase heterogeneous catalyzed processes using a variety of catalysts including neutral gamma —Al Og catalyst doped with an alkah metal (23), zinc aluminate (24,25), hthiated clays (26), Ca2(P0 2 montmorillonite clays (28). Dehydration of 2-methyl-1-butanol occurs over zinc aluminate catalyst at... 

Of the various inorganic soil constituents, smectites (montmorillonite clays) have the greatest potential for sorption of pesticides on account of their large surface area and abundance in soils. Weak base pesticides, both protonated and neutral species, have been shown to be sorbed as interlayer complexes. Sorption of atrazine on smectites ranges from 0 to 100% of added atrazine, depending on the surface charge density of the smectite (36). 

MeO)3CH, Montmorillonite Clay K-10, 5 min-15 h, >90% yield.Diethyl ketals have been prepared in satisfactoiy yield by reaction of the carbonyl compound and ethanol in the presence of montmorillonite clay. " ... 

E. C. Taylor and C.-S. Chiang, Synthesis, 467 (1977). Montmorillonite clay is activated Al203/Si02/H20. 

Allyl groups are subject to oxidative deprotection with Chromiapillared Montmorillonite Clay, -BuOOH, CH2CI2, isooctane, 85% yield. Allylamines are cleaved in 84—90% yield, and allyl phenyl ethers are cleaved in 80% yield. 

MeOH, Ce -exchanged Montmorillonite Clay, 25°, 0.5-12 h, 18-99% yield. Aldehydes can be selectively protected in the presence of ketones. ... 

HSCH2CH2SH, FeCb-Si02, CH2CI2, < 1 min-7 h."" Montmorillonite Clay can also be used as a support medium for the ferric ion (75-98% yield ). In this case, the reaction is chemoselective for aldehydes."" ... 

Newer catalysts for the PK synthesis include montmorillonite clays,... 

To obtain a high viscosity at a much lower clay concentration, certain water-soluble vinyl polymers called clay extenders can be used. In addition to increasing the yield of sodium montmorillonite, clay extenders serve as flocculants for other clay solids. The flocculated solids are much easier to separate using solids control equipment. 

The diagenetic effects are related to the alteration of rock mineral, shales in particular. Under certain conditions, montmorillonite clays change to illites, chlorites and kaolinites. The water of hydration that desorbs in the form of free water occupies a larger volume. This volume increase will cause abnormal pressures if the water cannot escape. 

Montmorillonite clays absorb water readily, swell greatly and confer highly plastic properties to a soil. Thus soil stress (Section 14.8) occurs most frequently in these soils and less commonly in predominantly kaolinitic types. Similarly, a soil high in bentonite will show more aggressive corrosion than a soil with a comparable percentage of kaolinite. A chalky soil usually shows low corrosion rates. Clay mineralogy and the relation of clays to corrosion deserves attention from corrosion engineers. Many important relationships are not fully understood and there is need for extensive research in this area. 

As an alternative to lithium enolates. silyl enolates or ketene acetals may be used in a complementary route to pentanedioates. The reaction requires Lewis acid catalysis, for example aluminum trifluoromethanesulfonate (modest diastereoselectivity with unsaturated esters)72 74 antimony(V) chloride/tin(II) trifluoromethanesulfonate (predominant formation of anti-adducts with the more reactive a,/5-unsaturated thioesters)75 montmorillonite clay (modest to good yields but poor diastereoselectivity with unsaturated esters)76 or high pressure77. 

Loss of surfactant due to adsorption onto the rock surface can also be minimized by blending the AOS with DPOS. This is shown in Fig. 28 which is a plot of the amount of surfactant adsorbed onto montmorillonite clay vs. the percentage of AOS in the blend. Clearly, when there is more than about 30% DPOS in the blend, total adsorption of surfactant is suppressed. 

Bioreactors containing an nndefined anaerobic consortinm rednced TNT to 2,4,6-triaminotoluene (TAT) in the presence of glncose (Dann et al. 1998). The sorption of TAT to montmorillonite clay was irreversible, and the snbstrate conld not be released by solvent extraction or by acid or alkaline treatment. Similar resnlts were obtained with humic acids in which covalent reactions with carbonyl or activated C=C bonding presumably occurred. Results from laboratory experiments nsing i C-labeled TNT in reactors to which... 

Bakke et al. (1982) have shown how montmorillonite catalyses chlorination and nitration of toluene nitration leads to 56 % para and 41 % ortho derivative compared to approximately 40 % para and 60 % ortho derivatives in the absence of the catalyst. Montmorillonite clays have an acidity comparable to nitric acid / sulphuric acid mixtures and the use of iron-exchanged material (Clayfen) gives a remarkable improvement in the para, ortho ratio in the nitration of phenols. The nitration of estrones, which is relevant in making various estrogenic drugs, can be improved in a remarkable way by using molecular engineered layer structures (MELS), while a reduction in the cost by a factor of six has been indicated. With a Clayfen type catalyst, it seems possible to manipulate the para, ortho ratio drastically for a variety of substrates and this should be useful in the manufacture of fine chemicals. In principle, such catalysts may approach biomimetic chemistry our ability to predict selectivity is very limited. 

A. Zaitoun and N. Berton. Stabilization of montmorillonite clay in porous media by high-molecular-weight polymers. In Proceedings Volume, pages 155-164. 9th SPE Formation Damage Contr Symp (Lafayette, LA, 2/22-2/23), 1990. 

Another possible alternative oxidant that has recently been investigated is an Fe(VI) species, potassium ferrate, K2Fe04, supported on montmorillonite clay.14 This reagent gives clean, high-yielding oxidation of benzylic and allylic alcohols, but saturated alcohols are less reactive. 

M. A., and Oueslati, R., Inactivation of cadmium induced immunotoxicological alterations in rats by Tunisian montmorillonite clay, Int Immunopharmacol, 7 (6), 750-760, 2007. 

As noted above, adsorption isotherms are largely derived empirically and give no information on the types of adsorption that may be involved. Scrivner and colleagues39 have developed an adsorption model for montmorillonite clay that can predict the exchange of binary and ternary ions in solution (two and three ions in the chemical system). This model would be more relevant for modeling the behavior of heavy metals that actively participate in ion-exchange reactions than for organics, in which physical adsorption is more important. 

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