Intercalates and exfoliates formed with monomeric amines and amides: composite materials containing same and methods of modifying rheology therewith

Intercalates formed by contacting a layered material, e.g., a phyllosilicate, with an intercalant monomer amine and/or amide to sorb or intercalate the intercalant monomer between adjacent platelets of the layered material. Sufficient intercalant monomer is sorbed between adjacent platelets to expand the adjacent platelets to a spacing of at least about 5 .ANG. (as measured after water removal to a maximum of 5% by weight water), up to about 100 .ANG. and preferably in the range of about 10-45 .ANG., so that the intercalate easily can be exfoliated into individual platelets. The intercalated complex can be combined with an organic liquid into a viscous carrier material, for delivery of the carrier material, or for delivery of an active compound; or the intercalated complex can be combined with a matrix polymer to form a strong, filled polymer matrix. Alternatively, the intercalated complex can be exfoliated prior to combination with the organic liquid or the matrix polymer.

FIELD OF THE INVENTION 
The present invention is directed to intercalated layered materials, and 
exfoliates thereof, manufactured by sorption (adsorption and/or 
absorption) of one or more functional monomeric organic compounds between 
planar layers of a swellable layered material, such as a phyllosilicate or 
other layered material, to expand the interlayer spacing of adjacent 
layers to at least about 5 Angstroms (.ANG.), preferably at least about 10 
.ANG.. More particularly, the present invention is directed to 
intercalates preferably having at least two layers of monomeric organic 
compounds sorbed on the internal surfaces of adjacent layers of the planar 
platelets of a layered material, such as a phyllosilicate, preferably a 
smectite clay, to expand the interlayer spacing to at least about 5 .ANG., 
preferably at least about 10 .ANG., more preferably to at least about 20 
.ANG., and most preferably to at least about 30-45 .ANG., up to about 100 
.ANG., or disappearance of periodicity. The intercalated layered materials 
preferably have at least two layers of amine and/or amide molecules sorbed 
on the internal surfaces between adjacent layers of the planar platelets 
of the layered material, such as a phyllosilicate, preferably a smectite 
clay. The resulting intercalates are neither entirely organophilic nor 
entirely hydrophilic, but a combination of the two, and easily can be 
exfoliated and combined as individual platelets with a polar organic 
solvent carrier to form a viscous composition having a myriad of uses. The 
resulting polar organic solvent carrier/intercalate or carrier/platelet 
composite materials are useful as plasticizers; for providing increased 
viscosity and elasticity to thermoplastic and thermosetting polymers; 
e.g., for plasticizing polyvinyl chloride; for food wrap having improved 
gas impermeability; electrical components; food grade drink containers; 
particularly for raising the viscosity of polar organic liquids; and for 
altering one or more physical properties of a matrix polymer, such as 
elasticity and temperature characteristics, e.g., glass transition 
temperature and high temperature resistance. 
BACKGROUND OF THE INVENTION AND PRIOR ART 
It is well known that phyllosilicates, such as smectite clays, e.g., sodium 
montmorillonite and calcium montmorillonite, can be treated with organic 
molecules, such as organic ammonium ions, to intercalate the organic 
molecules between adjacent, planar silicate layers, for bonding the 
organic molecules with a polymer, for intercalation of the polymer between 
the layers, thereby substantially increasing the interlayer (interlaminar) 
spacing between the adjacent silicate layers. The thus-treated, 
intercalated phyllosilicates, having interlayer spacings of at least about 
10-20 .ANG. and up to about 100 .ANG., then can be exfoliated, e.g., the 
silicate layers are separated, e.g., mechanically, by high shear mixing. 
The individual silicate layers, when admixed with a matrix polymer, 
before, after or during the polymerization of the matrix polymer, e.g., a 
polyamide--see U.S. Pat. Nos. 4,739,007; 4,810,734; and 5,385,776--have 
been found to substantially improve one or more properties of the polymer, 
such as mechanical strength and/or high temperature characteristics. 
Exemplary of such prior art composites, also called "nanocomposites", are 
disclosed in published PCT disclosure of Allied Signal, Inc. WO 93/04118 
and U.S. Pat. No. 5,385,776, disclosing the admixture of individual 
platelet particles derived from intercalated layered silicate materials, 
with a polymer to form a polymer matrix having one or more properties of 
the matrix polymer improved by the addition of the exfoliated intercalate. 
As disclosed in WO 93/04118, the intercalate is formed (the interlayer 
spacing between adjacent silicate platelets is increased) by adsorption of 
a silane coupling agent or an onium cation, such as a quaternary ammonium 
compound, having a reactive group which is compatible with the matrix 
polymer. Such quaternary ammonium cations are well known to convert a 
highly hydrophilic clay, such as sodium or calcium montmorillonite, into 
an organophilic clay capable of sorbing organic molecules. A publication 
that discloses direct intercalation (without solvent) of polystyrene and 
poly(ethylene oxide) in organically modified silicates is Synthesis and 
Properties of Two-Dimensional Nanostructures by Direct Intercalation of 
Polymer Melts in Layered Silicates, Richard A. Vaia, et al., Chem. Mater., 
5:1694-1696(1993). Also as disclosed in Adv. Materials, 7, No. 2: (1985), 
pp, 154-156, New Polymer Electrolyte Nanocomposites: Melt Intercalation of 
Poly(Ethylene Oxide) in Mica-Type Silicates, Richard A. Vaia, et al., 
poly(ethylene oxide) can be intercalated directly into Na-montmorillonite 
and Li-montmorillonite by heating to 80.degree. C. for 2-6 hours to 
achieve a d-spacing of 17.7 .ANG.. The intercalation is accompanied by 
displacing water molecules, disposed between the clay platelets, with 
polymer molecules. Apparently, however, the intercalated material could 
not be exfoliated and was tested in pellet form. It was quite surprising 
to one of the authors of these articles that exfoliated material could be 
manufactured in accordance with the present invention. 
Previous attempts have been made to intercalate polyvinylpyrrolidone (PVP), 
polyvinyl alcohol (PVA) and poly(ethylene oxide) (PEO) between 
montmorillonite clay platelets with little success. As described in Levy, 
et al., Interlayer Adsorption of Polyvinylpyrrolidone on Montmorillonite, 
Journal of Colloid and Interface Science, Vol. 50, No. 3, March 1975, 
pages 442-450, attempts were made to sorb PVP (40,000 average M.W.) 
between monoionic montmorillonite clay platelets (Na, K, Ca and Mg) by 
successive washes with absolute ethanol, and then attempting to sorb the 
PVP by contact with 1% PVP/ethanol/water solutions, with varying amounts 
of water, via replacing the ethanol solvent molecules that were sorbed in 
washing (to expand the platelets to about 17.7 .ANG.). Only the sodium 
montmorillonite had expanded beyond a 20 .ANG. basal spacing (e.g., 26 
.ANG. and 32 .ANG.), at 5.sup.+ % H.sub.2 O, after contact with the 
PVP/ethanol/H.sub.2 O solution. It was concluded that the ethanol was 
needed to initially increase the basal spacing for later sorption of PVP, 
and that water did not directly affect the sorption of PVP between the 
clay platelets (Table II, page 445), except for sodium montmorillonite. 
The sorption was time consuming and difficult and met with little success. 
Further, as described in Greenland, Adsorption of Polyvinyl Alcohols by 
Montmorillonite, Journal of Colloid Sciences, Vol. 18, pages 647-664 
(1963), polyvinyl alcohols containing 12% residual acetyl groups could 
increase the basal spacing by only about 10 .ANG. due to the sorbed 
polyvinyl alcohol (PVA). As the concentration of polymer in the 
intercalant polymer-containing solution was increased from 0.25% to 4%, 
the amount of polymer sorbed was substantially reduced, indicating that 
sorption might only be effective at polymer concentrations in the 
intercalant polymer-containing composition on the order of 1% by weight 
polymer, or less. Such a dilute process for intercalation of polymer into 
layered materials would be exceptionally costly in drying the intercalated 
layered materials for separation of intercalate from the polymer carrier, 
e.g., water, and, therefore, apparently no further work was accomplished 
toward commercialization. 
In accordance with one embodiment of the present invention, intercalates 
are prepared by contacting a phyllosilicate with a monomeric organic 
compound having an electrostatic functionality selected from the group 
consisting of amines; amides; and mixtures thereof. 
In accordance with an important feature of the present invention, best 
results are achieved using the monomeric organic compound, having at least 
one amine or amide functionality, in a concentration of at least about 2%, 
preferably at least about 5% by weight functional monomeric organic 
compound, more preferably at least about 10% by weight monomeric amine 
and/or amide, and most preferably about 30% to about 80% by weight, based 
on the weight of functional monomeric organic compound and carrier (e.g., 
water, with or without another solvent for the functional monomeric 
compound) to achieve better sorption of the functional monomeric organic 
compound between phyllosilicate platelets. Regardless of the concentration 
of functional monomeric organic compound in aqueous liquid, the 
intercalating composition should have a monomeric amine and/or 
amide:layered material ratio of at least 1:20, preferably at least 1:10, 
more preferably at least 1:5, and most preferably about 1:4 to achieve 
efficient intercalation of the functional monomeric organic compound 
between adjacent platelets of the layered material. The functional 
monomeric organic compound sorbed between and bonded to the silicate 
platelets probably via chelation-type bonding with the exchangeable 
cation, or like electrostatic or dipole/dipole bonding, causes separation 
or added spacing between adjacent silicate platelets and, for simplicity 
of description, both the amines and amides are hereinafter called the 
"intercalant" or "intercalant monomer" or "monomer intercalant". In this 
manner, the monomeric amines and/or amides will be sorbed sufficiently to 
increase the interlayer spacing of the phyllosilicate in the range of 
about 5 .ANG. to about 100 .ANG., preferably at least about 10 .ANG., for 
easier and more complete exfoliation, in a commercially viable process, 
regardless of the particular phyllosilicate or intercalant monomer. 
In accordance with the present invention, it has been found that a 
phyllosilicate, such as a smectite clay, can be intercalated sufficiently 
for subsequent exfoliation by sorption of organic monomer compounds that 
have an amine and/or an amide functionality to provide bonding of the 
amines and/or amides to the internal surfaces of the layered material by a 
mechanism selected from the group consisting of ionic complexing; 
electrostatic complexing; chelation; hydrogen bonding; dipole/dipole; Van 
Der Waals forces; and any combination thereof. Such bonding between two 
functional groups of one or two intercalant monomer molecules and the 
metal cations bonded to the inner surfaces of the phyllosilicate platelets 
provides adherence between the amine and/or amide molecules and the 
platelet inner surfaces of the layered material. Sorption and bonding of a 
platelet metal cation between two oxygen atoms of the intercalant monomer 
molecules increases the interlayer spacing between adjacent silicate 
platelets or other layered material to at least about 5 .ANG., preferably 
to at least about 10 .ANG., and more preferably at least about 20 .ANG., 
and most preferably in the range of about 30 .ANG. to about 45 .ANG.. Such 
intercalated phyllosilicates easily can be exfoliated into individual 
phyllosilicate platelets before or during admixture with a liquid carrier 
or solvent, for example, one or more monohydric alcohols, such as 
methanol, ethanol, propanol, and/or butanol; polyhydric alcohols, such as 
glycerols and glycols, e.g., ethylene glycol, propylene glycol, butylene 
glycol, glycerine and mixtures thereof; aldehydes; ketones; carboxylic 
acids; amines; amides; and other organic solvents, for delivery of the 
solvent in a thixotropic composition, or for delivery of any active 
hydrophobic or hydrophilic organic compound, such as a topically active 
pharmaceutical, dissolved or dispersed in the carrier or solvent, in a 
thixotropic composition; or the intercalates and/or exfoliates thereof can 
be admixed with a polymer or other organic monomer compound(s) or 
composition to increase the viscosity of the organic compound or provide a 
polymer/intercalate and/or exfoliate composition to enhance one or more 
properties of a matrix polymer. 
DEFINITIONS 
Whenever used in this Specification, the terms set forth shall have the 
following meanings: 
"Layered Material" shall mean an inorganic material, such as a smectite 
clay mineral, that is in the form of a plurality of adjacent, bound layers 
and has a thickness, for each layer, of about 3 .ANG. to about 50 .ANG., 
preferably about 10 .ANG.. 
"Platelets" shall mean individual layers of the Layered Material. 
"Intercalate" or "Intercalated" shall mean a Layered Material that includes 
a monomeric amine and/or monomeric amide molecules disposed between 
adjacent platelets of the Layered Material to increase the interlayer 
spacing between the adjacent platelets to at least about 5 .ANG., 
preferably at least about 10 .ANG.. 
"Intercalation" shall mean a process for forming an Intercalate. 
"Intercalant Monomer" or "Intercalant" shall mean a monomeric amine and/or 
a monomeric amide molecule that is sorbed between Platelets of the Layered 
Material and complexes with the platelet surfaces to form an Intercalate. 
"Intercalating Carrier" shall mean a carrier comprising water with or 
without an organic solvent used together with an Intercalant Monomer to 
form an Intercalating Composition capable of achieving Intercalation of 
the Layered Material. 
"Intercalating Composition" shall mean a composition comprising an 
Intercalant Monomer, an Intercalating Carrier for the Intercalant Monomer, 
and a Layered Material. 
"Exfoliate" or "Exfoliated" shall mean individual platelets of an 
Intercalated Layered Material so that adjacent platelets of the 
Intercalated Layered Material can be dispersed individually throughout a 
carrier material, such as water, a polymer, an alcohol or glycol, or any 
other organic solvent. 
"Exfoliation" shall mean a process for forming an Exfoliate from an 
Intercalate. 
SUMMARY OF THE INVENTION 
In brief, the present invention is directed to intercalates and exfoliates 
thereof formed by contacting a layered phyllosilicate with a functional 
organic monomer (intercalant monomer), having at least one amine or amide 
functionality, to sorb or intercalate the intercalant monomer or mixtures 
of intercalant monomers between adjacent phyllosilicate platelets. 
Sufficient intercalant monomer is sorbed between adjacent phyllosilicate 
platelets to expand the spacing between adjacent platelets (interlayer 
spacing) to a distance of at least about 5 .ANG., preferably to at least 
about 10 .ANG. (as measured after water removal, to a maximum water 
content of 5% by weight, based on the dry weight of the layered material) 
and more preferably in the range of about 30-45 .ANG., so that the 
intercalate easily can be exfoliated, sometimes naturally without shearing 
being necessary. At times, the intercalate requires shearing that easily 
can be accomplished, e.g., when mixing the intercalate with a polar 
organic solvent carrier, such as a polar organic hydrocarbon, and/or with 
a polymer melt to provide a platelet-containing composite material or 
nanocomposite--the platelets being obtained by exfoliation of the 
intercalated phyllosilicate. 
The intercalant monomer has an affinity for the phyllosilicate so that it 
is sorbed between, and is maintained associated with the silicate 
platelets, in the interlayer spaces, and after exfoliation. In accordance 
with the present invention, the intercalant monomer should include an 
amine and/or an amide functionality to be sufficiently bound, it is hereby 
theorized, by a mechanism selected from the group consisting of ionic 
complexing; electrostatic complexing; chelation; hydrogen bonding; 
dipole/dipole; Van Der Waals forces; and any combination thereof. Such 
bonding, via the metal cations of the phyllosilicate sharing electrons 
with two oxygen atoms from an amine or amide functionality of one 
intercalant monomer molecule or of two adjacent intercalant monomer 
molecules, to an inner surface of the phyllosilicate platelets provides 
adherence between the amine and/or amide molecules and the platelet inner 
surfaces of the layered material. Such intercalant monomers have 
sufficient affinity for the phyllosilicate platelets to maintain 
sufficient interlayer spacing for exfoliation, without the need for 
coupling agents or spacing agents, such as the onium ion or silane 
coupling agents disclosed in the above-mentioned prior art. A schematic 
representation of the charge distribution on the surfaces of a sodium 
montmorillonite clay is shown in FIGS. 1-3. As shown in FIGS. 2 and 3, the 
location of surface Na.sup.+ cations with respect to the location of 
oxygen (Ox), Mg, Si and Al atoms (FIGS. 1 and 2) results in a clay surface 
charge distribution as schematically shown in FIG. 3. The 
positive-negative charge distribution over the entire clay surface 
provides for excellent dipole-dipole attraction of polar amine and/or 
amide monomers on the surfaces of the clay platelets. 
The intercalate-containing and/or exfoliate-containing compositions can be 
in the form of a stable thixotropic gel that is not subject to phase 
separation and can be used to deliver any active materials, such as in the 
cosmetic, hair care and pharmaceutical industries. The layered material is 
intercalated and optionally exfoliated by contact with an intercalant 
monomer and water and then mixed and/or extruded to intercalate the 
monomer between adjacent phyllosilicate platelets and optionally separate 
(exfoliate) the layered material into individual platelets. The amount of 
water varies, depending upon the amount of shear imparted to the layered 
material in contact with the intercalant monomer and water. In one method, 
the intercalating composition is pug milled or extruded at a water content 
of about 25% by weight to about 50% by weight water, preferably about 35% 
to about 40% by weight water, based on the dry weight of the layered 
material, e.g., clay. In another method, the clay and water are slurried, 
with at least about 25% by weight water, preferably at least about 65% by 
weight water, based on the dry weight of the layered material, e.g., 
preferably less than about 20% by weight clay in water, based on the total 
weight of layered material and water, more preferably less than about 10% 
layered material in water, with the addition of about 2% by weight to 
about 90% by weight intercalant monomer, based on the dry weight of the 
layered material. 
Sorption of the intercalant monomer should be sufficient to achieve 
expansion of adjacent platelets of the layered material (when measured 
dry) to an interlayer spacing of at least about 5 .ANG., preferably to a 
spacing of at least about 10 .ANG., more preferably a spacing of at least 
about 20 .ANG., and most preferably a spacing of about 30-45 .ANG.. To 
achieve intercalates that can be exfoliated easily using the monomer 
intercalants disclosed herein, the weight ratio of intercalant monomer to 
layered material, preferably a water-swellable smectite clay such as 
sodium bentonite, in the intercalating composition should be at least 
about 1:20, preferably at least about 1:12 to 1:10, more preferably at 
least about 1:5, and most preferably about 1:5 to about 1:3. It is 
preferred that the concentration of intercalant monomer in the 
intercalating composition, based on the total weight of intercalant 
monomer plus intercalant carrier (water plus any non-amine and non-amide 
organic liquid solvent) in the intercalating composition is at least about 
15% by weight, more preferably at least about 20% by weight intercalant 
monomer, for example about 20-30% to about 90% by weight intercalant 
monomer, based on the weight of intercalant monomer plus intercalant 
carrier in the intercalant composition during intercalation. 
It has been found that the intercalates of the present invention are 
increased in interlayer spacing step-wise. If the phyllosilicate is 
contacted with an intercalant monomer-containing composition containing 
less than about 16% by weight intercalant monomer, e.g., 10% to about 15% 
by weight intercalant monomer, based on the dry weight of the 
phyllosilicate, a monolayer width of intercalant monomer is sorbed 
(intercalated) between the adjacent platelets of the layered material. If 
the phyllosilicate is contacted with an intercalating composition 
containing less than about 16% by weight intercalant monomer, e.g., 10% to 
about 15% by weight intercalant monomer, based on the dry weight of the 
phyllosilicate, a monolayer width of intercalant monomer is sorbed 
(intercalated) between the adjacent platelets of the layered material. A 
monolayer of intercalant monomer intercalated between platelets increases 
the interlayer spacing to about 5 .ANG. to less than about 10 .ANG.. When 
the amount of intercalant monomer is in the range of about 16% to less 
than about 35% by weight, based on the weight of the dry layered material, 
the intercalant monomer is sorbed in a bilayer, thereby increasing the 
interlayer spacing to about 10 .ANG. to about 16 .ANG.. At an intercalant 
monomer loading in the intercalant monomer-containing composition of about 
35% to less than about 55% intercalant monomer, based on the dry weight of 
the layered material contacted, the interlayer spacing is increased to 
about 20 .ANG. to about 25 .ANG., corresponding to three layers of 
intercalant monomer sorbed between adjacent platelets of the layered 
material. At an intercalant monomer loading of about 55% to about 80% 
intercalant monomer, based on the dry weight of the layered material in 
the intercalating composition, the interlayer spacing will be increased to 
about 30 .ANG. to about 35 .ANG., corresponding to 4 and 5 layers of 
intercalant monomer sorbed (intercalated) between adjacent platelets of 
the layered material. 
Such interlayer spacings have never been achieved by direct intercalation 
of the amine or amide intercalant monomers, without prior sorption of an 
onium or silane coupling agent, and provides easier and more complete 
exfoliation for or during incorporation of the platelets into a polar 
organic compound or a polar organic compound-containing composition 
carrier or solvent to provide unexpectedly viscous carrier compositions, 
for delivery of the carrier or solvent, or for administration of an active 
compound that is dissolved or dispersed in the carrier or solvent. Such 
compositions, especially the high viscosity gels, are particularly useful 
for delivery of active compounds, such as oxidizing agents for hair waving 
lotions, and drugs for topical administration, since extremely high 
viscosities are obtainable; and for admixtures of the platelets with polar 
solvents in modifying rheology, e.g., of cosmetics, oil-well drilling 
fluids, paints, lubricants, especially food grade lubricants, in the 
manufacture of oil and grease, and the like. Such intercalates also are 
especially useful in admixture with matrix thermoplastic or thermosetting 
polymers in the manufacture of polymeric articles from the polar organic 
carrier/polymer/intercalate and/or platelet composite materials. 
Once exfoliated, the platelets of the intercalate are predominantly 
completely separated into individual platelets and the originally adjacent 
platelets no longer are retained in a parallel, spaced disposition, but 
are free to move as predominantly individual intercalant monomer-coated 
(continuously or discontinuously) platelets throughout a carrier or 
solvent material to maintain viscosity and thixotropy of the carrier 
material. The predominantly individual phyllosilicate platelets, having 
their platelet surfaces complexed with intercalant monomer molecules, are 
randomly, homogeneously and uniformly dispersed, predominantly as 
individual platelets, throughout the carrier or solvent to achieve new and 
unexpected viscosities in the carrier/platelet compositions even after 
addition of an active organic compound, such as a cosmetic component or a 
medicament, for administration of the active organic compound(s) from the 
composition. 
As recognized, the thickness of the exfoliated, individual platelets (about 
10 .ANG.) is relatively small compared to the size of the flat opposite 
platelet faces. The platelets have an aspect ratio in the range of about 
200 to about 2,000. Dispersing such finely divided platelet particles into 
a polymer melt or into a polar organic liquid carrier imparts a very large 
area of contact between carrier and platelet particles, for a given volume 
of particles in the composite, and a high degree of platelet homogeneity 
in the composite material. Platelet particles of high strength and 
modulus, dispersed at sub-micron size (nanoscale), impart greater 
mechanical reinforcement and a higher viscosity to a polar organic liquid 
carrier than do comparable loadings of conventional reinforcing fillers of 
micron size, and can impart lower permeability to matrix polymers than do 
comparable loadings of conventional fillers.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
To form the intercalated and exfoliated materials of the present invention, 
the layered material, e.g., the phyllosilicate, should be swelled or 
intercalated by sorption of an intercalant monomer that includes an amine 
and/or an amide functionality. In accordance with a preferred embodiment 
of the present invention, the phyllosilicate should include at least 4% by 
weight water, up to about 5,000% by weight water, based on the dry weight 
of the phyllosilicate, preferably about 7% to about 100% water, more 
preferably about 25% to about 50% by weight water, prior to or during 
contact with the intercalant monomer to achieve sufficient intercalation 
for exfoliation. Preferably, the phyllosilicate should include at least 
about 4% by weight water before contact with the intercalating carrier for 
efficient intercalation. The amount of intercalant monomer in contact with 
the phyllosilicate from the intercalating composition, for efficient 
exfoliation, should provide an intercalant monomer/phyllosilicate weight 
ratio (based on the dry weight of the phyllosilicate) of at least about 
1:20, preferably at least about 3.2:20, and more preferably about 4-14:20, 
to provide efficient sorption and complexing (intercalation) of the 
intercalant monomer between the platelets of the layered material, e.g., 
phyllosilicate. 
The monomer intercalants are introduced in the form of a solid or liquid 
composition (neat or aqueous, with or without a non-amine and/or a 
non-amide organic solvent, e.g., an aliphatic hydrocarbon, such as 
heptane) having an intercalant monomer concentration of at least about 2%, 
preferably at least about 5% by weight intercalant monomer, more 
preferably at least about 50% to about 100% by weight intercalant monomer 
in the intercalating composition, based on the dry weight of the layered 
material, for intercalant monomer sorption. The intercalant monomer can be 
added as a solid with the addition to the layered material/intercalant 
monomer blend of about 20% water, preferably at least about 30% water to 
about 5,000% water or more, based on the dry weight of layered material. 
Preferably about 30% to about 50% water, more preferably about 30% to 
about 40% by weight water, based on the dry weight of the layered material 
is included in the intercalating composition when extruding or pug 
milling, so that less water is sorbed by the intercalate, thereby 
necessitating less drying energy after intercalation. The monomer 
intercalants may be introduced into the spaces between every layer, nearly 
every layer, or at least a predominance of the layers of the layered 
material such that the subsequently exfoliated platelet particles are 
preferably, predominantly less than about 5 layers in thickness; more 
preferably, predominantly about 1 or 2 layers in thickness; and most 
preferably, predominantly single platelets. 
Any swellable layered material that sufficiently sorbs the intercalant 
monomer to increase the interlayer spacing between adjacent phyllosilicate 
platelets to at least about 10 .ANG. (when the phyllosilicate is measured 
dry) may be used in the practice of this invention. Useful swellable 
layered materials include phyllosilicates, such as smectite clay minerals, 
e.g., montmorillonite, particularly sodium montmorillonite; magnesium 
montmorillonite and/or calcium montmorillonite; nontronite; beidellite; 
volkonskoite; hectorite; saponite; sauconite; sobockite; stevensite; 
svinfordite; vermiculite; and the like. Other useful layered materials 
include micaceous minerals, such as illite and mixed layered 
illite/smectite minerals, such as rectorite, tarosovite, ledikite and 
admixtures of illites with the clay minerals named above. 
Other layered materials having little or no charge on the layers may be 
useful in this invention provided they can be intercalated with the 
intercalant monomers to expand their interlayer spacing to at least about 
5 .ANG., preferably at least about 10 .ANG.. Preferred swellable layered 
materials are phyllosilicates of the 2:1 type having a negative charge on 
the layers ranging from about 0.15 to about 0.9 charges per formula unit 
and a commensurate number of exchangeable metal cations in the interlayer 
spaces. Most preferred layered materials are smectite clay minerals such 
as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, 
saponite, sauconite, sobockite, stevensite, and svinfordite. 
As used herein the "interlayer spacing" refers to the distance between the 
internal faces of the adjacent layers as they are assembled in the layered 
material before any delamination (exfoliation) takes place. The interlayer 
spacing is measured when the layered material is "air dry", e.g., contains 
3-10% by weight water, preferably about 3-6% by weight water, e.g., 5% by 
weight water based on the dry weight of the layered material. The 
preferred clay materials generally include interlayer cations such as 
Na.sup.+, Ca.sup.+2, K.sup.+, Mg.sup.+2, NH.sub.4.sup.+ and the like, 
including mixtures thereof. 
The amount of intercalant monomer intercalated into the swellable layered 
materials useful in this invention, in order that the intercalated layered 
material platelet surfaces sufficiently complex with the intercalant 
monomer molecules such that the layered material may be easily exfoliated 
or delaminated into individual platelets, may vary substantially between 
about 10% and about 90%, based on the dry weight of the layered silicate 
material. In the preferred embodiments of the invention, amounts of 
monomer intercalants employed, with respect to the dry weight of layered 
material being intercalated, will preferably range from about 8 grams of 
intercalant monomer:100 grams of layered material (dry basis), preferably 
at least about 10 grams of intercalant monomer:100 grams of layered 
material to about 80-90 grams intercalant monomer:100 grams of layered 
material. More preferred amounts are from about 20 grams intercalant 
monomer/100 grams of layered material to about 60 grams intercalant 
monomer/100 grams of layered material (dry basis). 
The monomer intercalants are introduced into (sorbed within) the interlayer 
spaces of the layered material in one of two ways. In a preferred method 
of intercalating, the layered material is intimately mixed, e.g., by 
extrusion or pug milling, to form an intercalating composition comprising 
the layered material, in an intercalant monomer/water solution, or 
intercalant monomer, water and an organic carrier for the amine or amide 
intercalant monomer. To achieve sufficient intercalation for exfoliation, 
the layered material/intercalant monomer blend contains at least about 8% 
by weight, preferably at least about 10% by weight intercalant monomer, 
based on the dry weight of the layered material. The intercalant monomer 
carrier (preferably water, with or without an organic solvent) can be 
added by first solubilizing or dispersing the intercalant monomer in the 
carrier; or a dry intercalant monomer and relatively dry phyllosilicate 
(preferably containing at least about 4% by weight water) can be blended 
and the intercalating carrier added to the blend, or to the phyllosilicate 
prior to adding the dry intercalant monomer. In every case, it has been 
found that surprising sorption and complexing of intercalant monomer 
between platelets is achieved at relatively low loadings of intercalating 
carrier, especially H.sub.2 O, e.g., at least about 4% by weight water, 
based on the dry weight of the phyllosilicate. When intercalating the 
phyllosilicate in slurry form (e.g., 900 pounds water, 100 pounds 
phyllosilicate, 25 pounds intercalant monomer) the amount of water can 
vary from a preferred minimum of at least about 30% by weight water, with 
no upper limit to the amount of water in the intercalating composition 
(the phyllosilicate intercalate is easily separated from the intercalating 
composition). 
Alternatively, the intercalating carrier, e.g., water, with or without an 
organic solvent, can be added directly to the phyllosilicate prior to 
adding the intercalant monomer, either dry or in solution. Sorption of the 
monomer intercalant molecules may be performed by exposing the layered 
material to dry or liquid intercalant monomers in the intercalating 
composition containing at least about 2% by weight, preferably at least 
about 5% by weight intercalant monomer, more preferably at least about 50% 
intercalant monomer, based on the dry weight of the layered material. 
Sorption may be aided by exposure of the intercalating composition to 
heat, pressure, ultrasonic cavitation, or microwaves. 
In accordance with another method of intercalating the intercalant monomer 
between the platelets of the layered material and exfoliating the 
intercalate, the layered material, containing at least about 4% by weight 
water, preferably about 10% to about 15% by weight water, is blended with 
an aqueous solution of an intercalant monomer in a ratio sufficient to 
provide at least about 8% by weight, preferably at least about 10% by 
weight intercalant monomer, based on the dry weight of the layered 
material. The blend then preferably is extruded for faster intercalation 
of the intercalant monomer with the layered material. 
The intercalant monomer has an affinity for the phyllosilicate so that it 
is sorbed between, and is maintained associated with the surfaces of the 
silicate platelets, in the interlayer spaces, and after exfoliation. In 
accordance with the present invention, the intercalant monomer should 
include an amine and/or an amide functionality to be sufficiently bound, 
it is hereby theorized, by a mechanism selected from the group consisting 
of ionic complexing; electrostatic complexing; chelation; hydrogen 
bonding; dipole/dipole; Van Der Waals forces; and any combination thereof. 
Such bonding, via the metal cations of the phyllosilicate sharing 
electrons with two nitrogen atoms from an amine or amide functionality of 
one intercalant monomer molecule or of two adjacent intercalant monomer 
molecules, to an inner surface of the phyllosilicate platelets provides 
adherence between the amine and/or amide molecules and the platelet inner 
surfaces of the layered material. Such intercalant monomers have 
sufficient affinity for the phyllosilicate platelets to maintain 
sufficient interlayer spacing for exfoliation, without the need for 
coupling agents or spacing agents, such as the onium ion or silane 
coupling agents disclosed in the above-mentioned prior art. 
As shown in FIGS. 1-3, the disposition of surface Na.sup.+ ions with 
respect to the disposition of oxygen (Ox) atoms, Mg, Si, and Al atoms, and 
the natural clay substitution of Mg.sup.+2 cations for Al.sup.+3 cations, 
leaving a net negative charge at the sites of substitution, results in a 
clay surface charge distribution as shown in FIG. 3. This alternating 
positive to negative surface charge over spans of the clay platelets 
surfaces, and on the clay platelet surfaces in the interlayer spacing, 
provide for excellent dipole-dipole attraction of polar amine and/or amide 
monomeric molecules for intercalation of the clay and for bonding of such 
polar molecules on the platelet surfaces, after exfoliation. 
It is preferred that the platelet loading be less than about 10%. Platelet 
particle loadings within the range of about 0.05% to about 40% by weight, 
preferably about 0.5% to about 20%, more preferably about 1% to about 10% 
of the composite material significantly enhances viscosity. In general, 
the amount of platelet particles incorporated into a liquid carrier, such 
as a polar solvent, e.g., a glycol such as glycerol, is less than about 
90% by weight of the mixture, and preferably from about 0.01% to about 80% 
by weight of the composite material mixture, more preferably from about 
0.05% to about 40% by weight of the mixture, and most preferably from 
about 0.05% to about 20% or 0.05% to about 10% by weight. 
In accordance with an important feature of the present invention, the 
intercalated phyllosilicate can be manufactured in a concentrated form, 
e.g., 10-90%, preferably 20-80% intercalant monomer with or without 
another polar organic compound carrier and 10-90%, preferably 20-80% 
intercalated phyllosilicate that can be dispersed in the polar organic 
carrier and exfoliated before or after addition to the carrier to a 
desired platelet loading. 
Polar organic compounds containing one or more amine or amide 
functionalities that are suitable for use as intercalate monomers and/or 
as the organic liquid carrier (matrix monomer) in accordance with the 
present invention include all organic amines and/or amides, such as the 
alkylamines; aminocycloalkanes and substituted aminocycloalkanes; 
cycloaliphatic diamines; 
fatty amines; and fatty amides. 
Amines and amides are suitable alone, or in admixture, as the intercalant 
monomer(s) and/or as the polar organic solvent carrier, for intercalation 
of the phyllosilicate and/or for admixture with the exfoliated individual 
platelets of the layered material in producing the nanocomposite of the 
present invention. The amines and amides can be any primary, secondary 
and/or tertiary amines or amides; including the lower aliphatic amines; 
alkylamines; cycloaliphatic amines or aminocycloalkanes and substituted 
aminocycloalkanes; cycloaliphatic diamines; fatty amines; aromatic amines 
including methylenedianiline and phenylenediamines; diaminotoluenes; 
diarylamines; alkanolamines; aniline and its derivatives. 
Examples of suitable amines that are useful as the intercalant monomer used 
for intercalation and exfoliation of the layered silicate materials, 
and/or as the polar organic carrier for admixture with the individual 
platelets in forming nanocomposite compositions are as follows: 
______________________________________ 
MOLECULAR SYNONYM OR COMMON 
ALKYLAMINES 
FORMULA ABBREVIATION 
______________________________________ 
methylamine 
CH.sub.5 N monomethylamine, 
aminomethane, MMA 
dimethylamine 
C.sub.2 H.sub.7 N 
DMA 
trimethylamine 
C.sub.3 H.sub.9 N 
N,N-dimethylmethanamine, 
TMA 
ethylamine C.sub.2 H.sub.7 N 
monoethylamine, 
aminoethane, MEA 
diethylamine 
C.sub.4 H.sub.11 N 
diethanamine, 
N-ethylethanamine, DEA 
triethylamine 
C.sub.6 H.sub.15 N 
TEA 
n-propylamine 
C.sub.3 H.sub.9 N 
mono-n-propylamine, 
1-aminopropane, 
propanamine, MNPA 
di-n-propylamine 
C.sub.6 H.sub.15 N 
N-propyl-1-propanamine, 
DNPA 
tri-n-propylamine 
C.sub.9 H.sub.21 N 
N,N-dipropyl-1- 
propanamine, TNPA 
isopropylamine 
C.sub.3 H.sub.9 N 
2-aminopropane, MIPA 
diisopropylamine 
C.sub.6 H.sub.15 N 
N-(1-methylethyl)-2- 
propanamine, DIPA 
allylamine C.sub.3 H.sub.7 N 
monoallylamine, 
3-aminopropene 
diallylamine 
C.sub.6 H.sub.11 N 
triallylamine 
C.sub.9 N.sub.15 N 
n-butylamine 
C.sub.4 H.sub.11 N 
mono-n-butylamine 
1-aminobutane, MNBA 
di-n-butylamine 
C.sub.8 H.sub.19 N 
N-butyl-1-butanamine, DNBA 
tri-n-butylamine 
C.sub.12 H.sub.27 N 
TNBA 
isobutylamine 
C.sub.4 H.sub.11 N 
monoisobutylamine, 
1-amino-2-methylpropane, 
MIBA 
diisobutylamine 
C.sub.8 H.sub.19 N 
2-methyl-N-(2- 
methylpropyl)-1- 
propanamine, DIBA 
triisobutylamine 
C.sub.12 H.sub.27 N 
TIBA 
sic-butylamine 
C.sub.4 H.sub.11 N 
2-aminobutane, 
1-methylpropanamine 
t-butylamine 
C.sub.4 H.sub.11 N 
2-aminoisobutane, 1,1- 
dimethylethanamine, 
trimethylaminomethane 
ethyl-n- C.sub.6 H.sub.15 N 
EBA 
butylamine 
dimethyl-n- 
C.sub.6 H.sub.15 N 
DMBA 
butylamine 
n-amylamine 
C.sub.5 H.sub.13 N 
di-n-amylamine 
C.sub.10 H.sub.23 N 
dipentylamine, 
dipentanamine 
tri-n-amylamine 
C.sub.15 H.sub.33 N 
tripentylamine, 
tripentanamine 
______________________________________ 
______________________________________ 
MOLECULAR 
CYCLOALIPHATIC AMINE FORMULA 
______________________________________ 
cyclopropylamine C.sub.3 H.sub.7 N 
cyclobutylamine C.sub.4 H.sub.9 N 
cyclopentylamine C.sub.5 H.sub.11 N 
cyclohexylamine C.sub.6 H.sub.13 N 
cycloheptylamine C.sub.7 H.sub.15 N 
cyclooctylamine C.sub.8 H.sub.17 N 
cyclododecylamine C.sub.12 H.sub.25 N 
______________________________________ 
______________________________________ 
MOLECULAR 
CYCLOALIPHATIC AMINE FORMULA 
______________________________________ 
1-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
2-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
(.+-.)cis-2-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
(.+-.)trans-2-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
(+)t-2-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
(-)t-2-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
3-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
(.+-.)cis-3-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
(.+-.)trans-3-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
4-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
cis-4-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
trans-4-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
3,3,5-trimethylcyclohexylamine 
C.sub.9 H.sub.19 N 
4-tert-butylcyclohexylamine 
C.sub.10 H.sub.21 N 
N-methylcyclohexylamine 
C.sub.7 H.sub.15 N 
N-ethylcyclohexylamine C.sub.8 H.sub.17 N 
N,N-dimethylcyclohexylamine 
C.sub.8 H.sub.17 N 
N,N-diethylcyclohexylamine 
C.sub.10 H.sub.21 N 
dicyclohexylamine C.sub.12 H.sub.23 N 
N-methyldicylohexylamine 
C.sub.13 H.sub.25 N 
1-adamantylamine C.sub.10 H.sub.17 N 
______________________________________ 
______________________________________ 
MOLECULAR 
DIAMINE FORMULA 
______________________________________ 
cis,trans-1,2-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
cis-1,2-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
(.+-.)trans-1,2-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
(+)trans-1,2-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
(-)trans-1,2-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
cis,trans-1,3-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
cis-1,3-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
trans-1,3-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
methylcyclohexanediamine 
C.sub.7 H.sub.16 N.sub.2 
cis,trans-1,3-cyclohexanediamine,2-methyl 
cis,trans-1,3-cyclohexanediamine,4-methyl 
cis,trans-1,4-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
cis-1,4-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
trans-1,4-cyclohexanediamine 
C.sub.6 H.sub.14 N.sub.2 
cis,trans-1,8-methanediamine 
C.sub.10 H.sub.22 N.sub.2 
cis,trans-1,3-di(aminomethyl)cyclohexane 
C.sub.8 H.sub.18 N.sub.2 
cis-1,3-di(aminomethyl)cyclohexane 
trans-1,3-di(aminomethyl)cyclohexane 
cis,trans-1,4-di(aminomethyl)cyclohexane 
C.sub.8 H.sub.18 N.sub.2 
cis-1,4-di(aminomethyl)cyclohexane 
C.sub.8 H.sub.18 N.sub.2 
trans-1,4-di(aminomethyl)cyclohexane 
cis,trans-isophoronediamine 
C.sub.10 H.sub.22 N.sub.2 
methylenedi(cyclohexylamine) 
C.sub.13 H.sub.26 N.sub.2 
isopropylidenedi(cyclohexylamine) 
C.sub.15 H.sub.30 N.sub.2 
3,3'-dimethylmethylene-di(cyclohexylamine) 
C.sub.15 H.sub.30 N.sub.2 
cis,trans-tricyclodecanediamine 
C.sub.12 H.sub.22 N.sub.2 
______________________________________ 
______________________________________ 
REPRESENTATIVE FATTY AMINES 
MOLECULAR 
FATTY AMINE FORMULA 
______________________________________ 
REPRESENTATIVE PRIMARY AMINES 
cocoalkylamines 
1-dodecylamine C.sub.12 H.sub.27 N 
1-hexadecylamine C.sub.16 H.sub.35 N 
1-octadecylamine C.sub.18 H.sub.39 N 
oleylamine C.sub.18 H.sub.37 N 
soyaalkylamines 
tallowalkylamines 
hydrogenated tallowalkylamines 
REPRESENTATIVE SECONDARY AMINES 
dicocoalkylamines 
di-n-dodecylamine C.sub.24 H.sub.51 N 
di-n-hexadecylamine C.sub.32 H.sub.67 N 
di-n-octadecylamine C.sub.36 H.sub.75 N 
ditallowalkylamines 
dihydrogenated tallowalkylamines 
REPRESENTATIVE TERTIARY AMINES 
Alkyldimethyl 
cocoalkyldimethylamines 
dimethyl-n-octylamine C.sub.10 H.sub.23 N 
dimethyl-n-decylamine C.sub.12 H.sub.27 N 
dimethyl-n-dodecylamine C.sub.14 H.sub.31 N 
dimethyl-n-tetradecylamine 
C.sub.16 H.sub.351eq N 
dimethyl-n-hexadecylamine 
C.sub.18 H.sub.39 N 
dimethyl-n-octadecylamine 
C.sub.20 H.sub.43 N 
dimethyloleylamine C.sub.20 H.sub.41 N 
Dialkylmethyl 
di-n-decylmethylamine C.sub.21 H.sub.45 N 
dicocoalylmethylamines 
dihydrogenated tallowalkylmethylamines 
Trialkyl 
tri-n-octylamine C.sub.24 H.sub.51 N 
tri-n-dodecylamine C.sub.36 H.sub.75 N 
tri-n-hexadecylamines 
______________________________________ 
Nanocomposite Uses 
Fatty amines and chemical products derived from the amines are used in many 
industries. Uses for the nitrogen derivatives are as follows: fabric 
softeners, oil field chemicals, asphalt emulsifiers, petroleum additives, 
and mining. 
Amine salts, especially acetate salts prepared by neutralization of a fatty 
amine with acetic acid, are useful as flotation agents (collectors), 
corrosion inhibitors, and lubricants. 
A significant use of ethoxylated and propoxylated amines is as antistatic 
agents in the textile and plastics industry. Ethoxylates are also used in 
the agricultural area as adjuvants. Examples of uses for amine oxides 
include: detergent and personal care areas as a foam booster and 
stabilizer, as a dispersant for glass fibers, and as a foaming component 
in gas recovery systems. 
Important uses for the diamines include: corrosion inhibitors, flotation 
agents, pigment wetting agents, herbicides, and asphalt emulsifiers. 
Fatty amines and derivatives are widely used in the oil field, as corrosion 
inhibitors, surfactants, emulsifying/deemulsifying and gelling agents. In 
the mining industry, amines and diamines are used in the recovery and 
purification of minerals, flotation, and benefication. A significant use 
of fatty diamines is as asphalt emulsifiers for preparing asphalt 
emulsions. Diamines have also been used as epoxy curing agents, corrosion 
inhibitors, gasoline and fuel oil additives, and pigment wetting agents. 
In addition, derivatives of the amines, amphoterics, and long-chain 
alkylamines are used as anionic and cationic surfactants in the personal 
care industry. 
Aromatic Amines 
Aniline and its derivatives: Aniline (benzenamine) is the simplest of the 
primary aromatic amines. 
Representative Aniline Derivatives 
______________________________________ 
REPRESENTATIVE ANILINE DERIVATIVES 
MOLECULAR