CA2186196A1 - Intercalates and exfoliates formed with organic pesticide compounds and compositions containing the same - Google Patents

Abstract

Intercalates formed by contacting an activated layered material, e.g., an activated phyllosilicate, with an intercalant pesticide to intercalate an intercalant pesticide between adjacent platelets of the layered material is disclosed. Sufficient intercalant pesticide 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 to about 45 .ANG., so that, if desired, the intercalate can be exfoliated into individual platelets. The intercalate can be combined with an organic liquid to form a viscous composition for delivery of a pesticide compound.
Alternatively, the intercalate can be exfoliated prior to combination with the organic liquid. The intercalated complex also can be admixed with solid particles to provide a granular, dust, or wettable powder pesticide composition.

Description

-218~1 9~
PATENT APPLICATION
28682/128~.A
TNrpor~r~rc AND ~FOLIATE8 FORMED WITH
ORGAIIIC PE:RTICIDE ._ ~ AND
_____ ~ THE 8AME
FIELD OF ~u~z ~
The present invention is directed to inter-calated pesticides manufactured by intercalation of one or more organic pesticide, '- between planar layers of a swellable layered material. More particu-larly, the present invention is directed to interca-lates having at least one layer of organic pesticide ' sorbed on the internal surfaces of adjacent layer6 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 A, preferably at least about 10 A, more preferably to at least about 20 ~, and most preferably to at least about 30 A, up to about 100 A, or disd~eaLal-ce of periodicity. The intercalated layered materials have at least one layer of pesticide ~ ' sorbed on the internal surfaces between adjacent layers of the planar platelets of the layered material. The result-ing intercalates are a combination of or~n~rhil;c and hydrophilic, and, if desired, can be exfoliated to individual platelets. The intercalates or eYfoliates can be combined with an organic solvent to ~orm a viscous pesticide composition or a thixotropic gel.

t ~ ~186196 - 2 - PAT~5NT Appr~Tr~Tr 28682/ 128~A
OF T}l:E l~ v ~r~ AND PRIOR ART
Calcined clays traditionally have been used as carriers for granular pesticides. Granular pesti-cides having a calcined clay carrier are limited 5 because such carriers can il~ ' te no more than about 10% by weight of a pesticide. The amount of pesticide i5 limited because the pesticide merely enters the pore structure of the calcined clay. ~hen the available sites in the pore 5LLU~.LUL~ are filled, 10 then no further pesticide can be held by the calcined clay. If the available surface area of the carrier was greater, the amourlt of pesticide in a granular product could be increased up to about 30% to 40% by weight of the pesticide granule.
It also is well known that phyllosilicates, such as smectite clays, e.g. l sodium montmorillonite and calcium montmorillonite, can be treated with organic molecules ~ such as organic i i llm ions, to intercalate organic molecules between adjacent, planar 20 silicate layers, for bonding the organic molecules with a polymer to intercalate the polymer between the layers, thereby substantially increasing the inter-layer (interlaminar) spacing between the adjacent silicate layers. The thus-treated, intercalated 25 phyllosilicates, having interlayer SFAr-i n~s of at least about 10 A and up to about 100 A, then can be exfoliated, i.e., the silicate layers are separated, e . g ., mechanically , by high shear mixing . The indi-vidual silicate layers, when admixed with a matrix 30 polymer, before, after or during the polymerization of the matrix polymer, e.g., a polyamide--see U.s. Patent Nos. 4,739,007; 4,310,734; and 5,385,776--have been i . ~
2!~6196 - 3 - PATENT AppT TC
28682/128~A
found to substantially improve one or more properties of the polymer, such as mechanical strength and/or high temperature characteristics.
Examples of such prior art composites, also 5 called ~'n~n~ - , -sites, " are di6closed in published PCT disclosure WO 93/04118 and U.S. Patent No.
5, 385, 776, disclosing the admixture of individual platelet particles derived from intercalated layered silicate materials, with a polymer to form a polymer 10 matrix having one or more properties of the matrix polymer i uv.:d by the addition of the exfoliated intercalate. As disclosed in WO 93/04118 l the inter-calate is formed (the interlayer spacing between adjacent silicate platelets is increased) by adsorp-15 tion of a silane coupling agent or an onium cation,such as a ~juaternary ammonium _ uild, having a reactive group which is compatible with the matrix polymer. Such ajuaternary ammonium cations are well known to convert a highly hydrophilic clay, such as 20 sodium or calcium montmorillonite, into an organo-philic clay capable of sorbing organic molecules.
- A publication that discloses direct interca-lation (without solvent) of polystyrene and poly(ethylene oxide~ in organically ~nodified silicates 25 is Richard A. Vaia et al., "Synthesis and Properties ûf Tl~ro-Dimensional NanostL-uctures by Direct Intercala-tion of Polymer Melts in ~ayered Silicates, " Chem.
Mater., 5:1694-1696(1993). Also, as disclosed in Richard A. Vaia et al., "New Polymer ELectrolyte Nano-30 composites: Melt Intercalation of PolytEthylene Oxide)in Mic~-Type Silic~tes, " Adv. Materials, 7, No. 2:
(1985), pp. 154-156, poly(ethylene oxide) can be intercalated directly into sodium (Na) montmorillonite -~ 2~6196 - 4 - PATENT APPLICATIO!I
28682/128~A
and lithium (Li) montmorillonite by heating to 80~C
for 2-6 hours to achieve a d-spacing of 17 . 7 A. The intercalation is ~: -n;ed by displacing water molecules, rl i cp,.c~.9 between the clay platelets, with 5 polymer molecules. Apparently, however, the interca-lated material could not be exfoliated and was tested in pellet form. It was quite surprising to one of the authors of these articles that eYfoliated material could be manufactured in accordance with the present 10 invention.
Previous attempts to intercalate polyvinyl-pyrrolidone (PVP), polyvinyl alcohol (PVA) and poly(ethylene oxide) (PEO) between montmorillonite clay platelets met with little success. As described 15 in Levy et al., "Interlqyer Adsorption of Polyvinyl-pyrrolidone 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. 3 between monoionic montmorillonite clay 20 platelets (Na, K (potassium), Ca (calcium), and Mg (magnesium) ) 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 (H2O), via replacing the 25 ethanol solvent molecules that were sorbed in washing (to expand the platelets to about 17 . 7 A) . Only the sodium montmorillonite had ~Yr~n~d beyond a 20 A
basal spacing (e.g., 26 A and 32 A), at 5+% H2O, after contact with the PVP/ethanol/H2O solution. It was 30 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), 1 ..
21 861 ~
-- 5 -- PATl~NT APPLICATI01~
286821128~A
except for sodium montmorillonite. The sorption was time cnn~l~m;n~ and difficult and met with little succes6 .
Further, as described in Greenland, "Adsorp-5 tion of Polyvinyl Alcohols by Montmorillonite, "
JournP1 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 A due to the sorbed polyvinyl alcohol (PVA).
10 As the ;:onctl,~L~ tion of polymer in the intercalant poly -c.ull~aining solution was increased from 0 . 25%
to 496, the amount of polymer sorbed was 6ubstantially reduced, indicating that sorption might only be effective at polymer concentrations in the intercalant 15 poly cu--Laining composition on the order of 196 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 20 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 25 contacting a phyllosilicate either with water, or with an aqueous solution of a water-601uble polymer and/or a water-miscible organic solvent, like an alcohol, followed by contact with a monomeric organic pesticide _I.d or a solution of a pesticide _ '.
30 Typically, the pesticide ' has a polar organic moiety, such as a carbonyl functionality, like, for example, a carboxylic acid, or salt thereof, an ester, an amide, an aldehyde, a ketone, or a mixture thereof.

~ . ~
~186196 - 6 - PATENT Appr.Tr 28682/ ~ 284A
The pesticide also can contain other polar organic moieties in addition to, or in place of, the carbonyl functionality, such as, for example, a sulfur-oxygen moiety, a phosphorus-oxygen moiety, a cyano moiety, or 5 a nitro moiety. If the intercalate is prepared using an aqueous solution of a water-soluble polymer and/or a water-miscible organic solvent, then nonpolar pesticides, like chlordane and lindane, can be inter-calated between clay platelets.
The addition of a pesticide or pesticide solution displaces the water and water-soluble poly-mer, if present, ~ =pos~ between the clay platelets of the intercalate. The pesticide, therefore, dis-places the water and water-soluble polymer between the 15 clay platelets. The intercalated pesticide then is dried to remove the water, and pelletized to provide a granular pesticide containing up to 40% by weight of a pesticide.
In accordance with an important feature of 20 the present invention, best results are achieved by using an aqueous solution of a water-soluble polymer, like polyvinylalcohol, and/or a water-miscible organic solvent, to first intercalate, i.e., activate, the clay, then using an organic pesticide ~ _ having 25 at least one polar organic moiety, and preferably a carbonyl functionality, in a concentration of at least about 2%, preferably at least about 5%, more pre~era-bly at least about 10%, by weight, based on the weight of organic pesticide compound and carrier (e. g., 30 water, an organic solvent for the pesticide Ju--d, or a mixture thereof ) to achieve better sorption of the organic pesticide compound between phyllosilicate platelets. If the pesticide is a solid at intercalat-i .~
218619~

- 7 - PATENT AppT Tl'~
28682/128~A
ing temperature, it can be dissolved in a solvent. If the pesticide is a liquid ~_ ' at intercalating temperature, the pesticide can be intercalated between phyllosilicate platelets without using a solvent.
Regardless of the concentration of organic pesticide compound in a solvent, a water-soluble poly-mer:layered material ratio of at least 1:20, prefera-bly at least 1:10, more preferably at least 1:4, and most preferably about 1:2, by weight, achieves effi-cient intercalation of the organic pesticide c between adjacent platelets of the layered material.
A water-miscible organic solvent can be used in place of the water-soluble polymer. It has been theorized that water, or aqueous solution of water-soluble polymer, intercalates between the clay layers to activate the clay, then the organic pesticide ~ ,uu--d displaces the water and water-soluble polymer and is bonded to the silicate platelets via chelation-type bonding with the exchangeable cation, or via electro-static-or dipole/dipole bonding. The sorption of the water and/or water-soluble polymer, causes separation or added spacing between adjacent silicate platelets.
An extrusion process accelerates intercalation of the pesticide between a'ctivated clay platelets.
For simplicity of description, all organic pesticide _ -c are hereinafter termed an "inter-calant pesticide. " The water-soluble polymers are hereinafter termed an "intercalant polymer. " In this manner, the water-soluble polymers, and subsequently 3 0 the organic pesticides, are suf f iciently sorbed to increase the interlayer spacing of the phyllosilicate in the range of about 5 A to about 100 A, preferably at least about 10 A, for e~sier and more complete ~ .~
2~86196 28682/128~A
exfoliation, if desired, in a commercially viable proces6, regardless of the particular phyllosilicate or intercalant pesticide.
In accordance with the present invention, it has been found that a phyllosilicate, such as a smectite clay, that has been activated with water or an aqueous solution of a water-soluble polymer and/or a water-miscible organic solvent, can be intercalated by sorption of organic pesticide _ -c having a polar moiety, liXe carbonyl functionality, to provide bonding of the polar moiety to the internal surfaces of the layered material by a r--h;~nicm cF~ rt~d from the group consisting of ionic complexing, electrostat-ic complexing, chelation, l~ydr~ bonding, dipole/-dipole interaction, Van Der Waals forces, and any combination thereof. Such bonding between the polar moieties of one or two intercalant pesticide molecules and the metal cations bonded to the inner surf aces of the phyllosilicate platelets provides adherence between the organic pesticide molecules and the platelet inner surf aces of the layered material .
Activation of the clay and sorption and bonding of a platelet metal cation between two electronegative atoms of the intercalant pesticide molecules, like oxygen, sulfur, or nitrogen, for example, increases the interlayer spacing between adjacent silicate platelets or other layered material to at least about 5 A, preferably to at least about 10 A, and more prefer~bly at least about 20 A, and most preferably in the range of about 30 A to about 100 A. In addition, if a water-soluble polymer is used to activate the phyllosilicate, the intercalant polymer provides suf f icient interlayer spacing such that pesticides ~ . ~
~1 861 9~
-- 9 -- PATE~T APPr Tr~TT

lacking a polar group can be intercalated into the clay.
The intercalated clay ~ r nt~; n i n~ a pesti-cide , i . e ., intercalated pesticide product , can be 5 used directly a6 a pesticide product. The intercalat-ed pesticide also can be used as the active ingredient in a granular, dust, or wettable powder pesticide composition by admixture of the solid pesticide inter-calant with ingredients well known in the art.
Such intercalated pesticides also easily can be exfoliated, if desired, into individual phyllo-silicate platelets before or during admixture with a liquid carrier or solvent, for example, one or more dL iC alcohols, such as methanol, ethanol, 15 propanol, and/or butanol, polyhydric alcohols, such as glycerols and glycols, e.g., ethylene glycol, propyl-ene glycol, butylene glycol, glycerine, and mixtures ~hereof, aldehydes, ketones, carboxylic acid esters, amines, llyd~u-~y~LIlers, like ethylene glycol monobutyl 20 ether, glycol ether esters, like cellosolve acetate, aromatic or aliphatic IIYd1U~-CLLbUILS~ and other organic solvents, like DNS0, DMF, or HMPA. The exfoliated platelets can be used for delivery of any active llydLu~hobic or hydrophilic organic pesticide - , 25 such as a contact or a systemic pesticide ~ .d, dissolved or dispersed in the carrier or solvent to provide either a solid, as a granular, dust, or wettable powder, or a thixotropic composition.
nr...lNl~r_ -Whenever used in this specification, the terms set forth shall have the following r-~n;n~c ~' 2~86~96 - 10 - PATEI~T App 28682/128~.~
"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 th;r~n~cc, for each layer, of about 3 A to about 5 50 A, preferably about 10 ~.
"Platelets" shall mean individual layers of the layered material.
"Intercalate" or "Intercalated" shall mean a layered material that i nrlllA~.c a water-soluble 10 polymer or an organic pesticide ~ d i cpO5~
between adjacent platelets of the layered material to increase the interlayer spacing between the adjacent platelets to at least about 5 ~, preferably at least about 10 ~.
"Intercalated Pesticide Product" shall mean an intercalated clay containing a pesticide.
"Intercalation" shall mean a process for forming an intercalate.
"Intercalant Pesticide" shall mean a pesti-20 cide ' having a polar moiety that is sorbedbetween platelets of the layered material and complex-es with the platelet surfaces to form an intercalate.
"Intercalant Polymer" shall mean a water-soluble polymer that is sorbed between platelets of 25 the layer material, expands the space between the platelet materials, and complexes with the platelet surfaces to form an intercalate.
"Intercalating Carrier" shall mean a carrier comprising water with or without an organic solvent 30 used together with an intercalant pesticide to form an intercalating composition capable of achieving inter-calation of the layered material.

~ . ~

"Intercalating Composition" shall mean a composition comprising an intercalant pe6ticide, an intercalating carrier for the intercalant pesticide, and a layered material.
"Exfoliate" or "Exfoliated" shall mean individual platelets of an intercalated layered material 80 that adjacent platelets of the intercalat-ed layered material can be di6persed individually throughout a carrier material, such as a solid carri-er, water, an alcohol or glycol, or any other organic solvent .
"Exfoliation" shall mean a process for forming an exfoliate from an intercalate.
DY OF ~'TiF ~ hy~
In brief, the present invention is directed to intercalates, and to exfoliates therefrom, formed by contacting a layered phyllosilicate with water or an aqueous 601ution of a water-soluble polymer and/or a water-miscible organic solvent, and with an organic 20 pesticide (i.e., intercalant pesticide), typically having at least one polar moiety, to sorb or interca-late the intercalant pesticide, or mixture of inter-calant pesticides, between adjacent phyllosilicate platelets. Sufficient intercalant pesticide is sorbed 25 between adjacent phyllosilicate platelets to expand the spacing between adjacent platelets (interlayer spacing) to a distance of at least about 5 A, prefera-bly to at least about 10 ~ (as measured after water removal, to a maximum water content of 59~ by weight, 30 based on the dry weight of the layered material) and more preferably in the range of about 20 ~ to about 45 2~8519~
- 12 - PATENT Appr~T
2868Z/lZ8~A
A. The intercalate, after drying, contain6 up to about 40% by weight pesticide. If desired, the intercalate can be eYfoliated easily, 60metimes naturally, i.e., without shearing. At times, the 5 intercalate requires shearing that can be accomplished easily, e.g., when mixing the intercalate with an organic solvent carrier, such as an organic hydro-carbon, the platelets are obtained by exfoliation of the intercalated phyllosilicate.
The intercalant pesticide has an affinity for the phyl l osil; r ate so that it eYpels water and intercalant polymer, is sorbed between silicate platelets, and is maintained associated with the silicate platelets in the interlayer spaces, even 15 after exfoliation. In accordance with the present invention, the intercalant pesticide typically in-cludes a polar moiety, for example a carbonyl func-tionality, like a carboxylic acid, to be sufficiently bound between clay platelets by a r~ n i ~ ~ selected 20 from the group consisting of ionic complexing, elec-trostatic complexing, chelation, ilydLu~ell bonding, dipoleldipole interactions, Van Der Waals forces, and any combination thereof. H~wever, the pesticide can be free of a polar moiety if thë phyllosilicate first 25 is actlvated by contact with an aqueous solution of a water-soluble polymer, i.e., an intercalant polymer.
Such bonding, via metal cations of the phyllosilicate sharing electrons with two ele- ~Lu..eyrl-tive atoms of one intercalant pesticide molecule or 30 with two adjacent intercalant pesticide molecules, to an inner surface of the phyllosilicate platelets provides adherence between the pesticide molecules and the platelet inner surfaces of the layered material.

~ .~

28682/128~.A
The ele~-LL~lleyative atoms can be, for example, oxygen, sulfur, nitrogen, and combinations thereof. Atoms having a sufficient ele~:~L~,..e~-tivity to bond to metal cations on the inner surface of the platelets prefera-5 bly have an ele.:LL~.Ie~tivity of at least 2.0, andmore preferably at least 2.5 on the Pauling Scale. A
"polar moiety" or "polar group" is defined as a moiety having two adjacent atoms that are bonded covalently and preferably have a difference in ele~;LLo~.ey<ltivity 10 of at lea6t 0.5 electronegativity units on the Pauling Scale. Intercalant pesticides having a polar moiety have sufficient affinity for the phyllosilicate platelets to maintain sufficient interlayer spacing for exfoliation, without the need for coupling agents 15 or spacing agents, such as the onium ion or silane coupling agents disclosed in the abu~,~ Lioned prior art. Intercalant pesticides lacking a polar moiety enter the space between two adjacent platelets because of the relatively large spacing provided by an inter-20 calant polymer during activation of the clay.
A schematic representation of the chargedistribution on the surfaces of a sodium montmorillo-nite clay is shown in Figs. 1-3. As shown in Figs. 2 and 3, the location of surface Na (sodium) cations 25 with respect to the location of o (oYygen), Mg (magne-sium), Si (silicon), and Al (aluminum) 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 30 surface provides for ~~Y~ nt dipole-dipole attrac-tion of pesticide 'c: having a polar moiety on the surfaces of the clay platelets.

~ .~

Intercalate-containing and/or exfoliate-con-taining compositions can be in the form of a 601id, or a viscous liquid or stable thixotropic gel, that is not subject to phase separation. Either form can be 5 used to deliver the active pesticide, '. In either-form, the layered material is activated, then intercalated by contact with an intercalant pesticide, by miYing and/or extruding, to intercalate the pesti-cide between adjacent phyllosilicate platelets, and 10 finally, optionally, separating (i.e., exfoliating) the intercalated layered material into individual platelets .
The amount of water and intercalant polymer used during the activation process varies, ~PrPn~;n~
15 upon the amount of shear imparted to the layered material during contact with the intercalant pesticide ~nd solvent. In one method, the layered material is pug milled or extruded at a water content ~with or without a water-soluble polymer) of about 25% by 20 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 . Typical-ly, a water-miscible organic solvent is present to ~ssist the water activate the clay. An organic 25 solvent often is not present if a water-soluble polymer is used.
In another method, the clay and water (or aqueous solution of intercalant polymer and/or water-mi~c;hlP organic solvent) are slurried, with at least 30 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 .~. 21~6196 layered material and water, more preferably less than about 10% layered material in water, with the subse-quent addition of about 2% by weight to about 90% by weight intercalant pesticide, based on the dry weight of the layered material, after activation of the clay.
Activation of the clay and 60rption of the intercalant pesticide should be suf f icient to achieve p;~nc;~n of adjacent platelets of the layered materi-al (when measured dry) to an interlayer spacing of at - 10 least about 5 A, preferably to a spacing of at least about 10 A, more preferably a spacing of at least about 20 A, and most preferably a spacing of about 30 A to about 45 A. To achieve intercalates that can be exfoliated easily using the pesticide intercalants disclosed herein, the weight ratio of intercalant pesticide 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 1:4, and most preferably about 1: 3 . It is pref erred that the concentration of intercalant pesticide, based on the total weight of intercalant pesticide plus intercalant carrier ( i . e ., water plus any organic liquid solvent) is at least about 15% by weight, more preferably at least about 20% by weight, intercalant pesticide, for example about 20% to about 90% by weight intercalant pesti-cide, based on the weight of intercalant pesticide plus intercalant carrier during intercalation.
The intercalates of the present invention are increased in interlayer spacing step-wise. If the phyllosilicate is contacted with an intercalant poly _u-lLaining or an intercalant pesticide-con--- 2186~96 taining composition containing less than about 16% by weight intercalant polymer or pesticide, e.g., 10% to about 15% by weight, based on the dry weight of the phyl l o~ cate~ a monolayer width of intercalant 5 polymer or pesticide is sorbed (i.e., intercalated) between the adjacent platelets of the layered materi-al. A monolayer of intercalant intercalated between platelets increases the interlayer spacing to about 5 A to less than about 10 A. When the amount of inter-10 calant pesticide, or intercalant polymer, is in therange of about 16% to less than about 35% by weight, based on the weight of the dry layered material, the intercalant is sorbed in a bilayer, thereby increasing the interlayer spacing to about 10 A to about 16 A.
15 At an intercalant pesticide, or intercalant polymer, loading of about 35% to less than about 55% inter-calant, based on the dry weight of the layered materi-al contacted, the interlayer spacing is increased to about 20 A to about 25 A, CULL~ ;n~ to three 20 layers of intercalant sorbed between adjacent plate-lets of the layered material. At an intercalant loading of about 55% to about 80% intercalant, based on the dry weight of the layered material, the inter-layer spacing will be increased to about 30 A to about 25 35 A, C~JLL ~ inq to 4 and 5 layers of intercalant sorbed (i.e., intercalated) between adjacent platelets of the layered material.
Such interlayer spar~inqc: have never been achieved by direct intercalation of intercalant 30 polymers or intercalant pesticides, 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 carrier . .
21 ~6 1 9~
-- 17 -- PATEI~T APPLICATIO~
28682/128~.A
or 601vent, to provide unexpectedly viscous liquid compositions for delivery of an active pe6ticide that is dispersed in the carrier or solvent. Such composi-tions, ~p-~;Ally the high vi6c06ity thixotropic gel6, 5 are particularly u6eful pe6ticide compo6ition6 because the enviL, ~al and toxicological danger6 a660ciated with 6pill6 and 6pill clean-up of liquid pe6ticide6 are UVe:L~ -. The thixotropic, high vi6cosity gel6 are ea6y to confine and collect if 6pilled. In addition, the thixotropic gel6 can be di6601ved or di6per6ed in an appropriate 601vent by a pe6ticide applicator to provide a 6pray 601ution.
After exfoliation of the intercalates, the platelets of the intercalate are prPd~ ; n~ntly com-15 pletely separated into individual platelets and theoriginally adjacent platelets no longer are retained in a parallel, spaced disposition, but are free to move as prPd~m;nAntly individual intercalant pesti-cide-coated (either continuously or discontinuously) 20 platelets thIuuylluuL a carrier or 601vent material to maintain viscosity and thixotropy of the carrier material. The prPcl~-;nAntly individual phyllosilicate platelets, having their platelet surfaces complexed with intercalant pesticide molecules, are randomly, 25 homogeneously and uniformly di6persed, pr~ inAntly as individual platelets, throughout the carrier or solvent to achieve new and ""~ viscosities in the carrier/platelet compositions even after zlddition of additional active organic ~ '-, such as a 30 second pesticide or a pesticide adjuvant, for adminis-tration of the intercalant pesticide and additional active organic ~ _ 'c from the composition.

. . ~

- 18 -- PAq~E~rr AppT-28682/128~A
A6 recognized, the thickne66 of the exfoli-ated, individual platelet6 (about 10 A) is relatively 6mall ~ d to the 6ize of the flat oppo6ite platelet faces. The platelets have an aspect ratio in the range of about 200 to about 2,000. Dispersing such finely divided platelet particle6 into an organic liquid carrier impart6 a very large area of contact between carrier and platelet particles, for a given volume of particles, and a high degree of platelet hl , -;ty in the compo6ition. Platelet particle6 of high ~LL~I~yLh and modulu6, disper6ed at 6ub-micron size (n In-~s~ e), impart a higher vi6c06ity to an organic liquid carrier than do comparable loading6 of conventional particle6 of micron size.
P~rT~ E~ T ~__ OF ~rT~ r o7~ TNÇ:S
Fig. 1 is a schematic repre6entation of a top view (ab-projection) of two layers of sodium montmorillonite clay showing the upper oxygen atom6 of silicon tetrahedral sheet with sodium cations in hr.Y_~J.n:~l holes and octahedral cations of ~ minllm and magnesium;
Fig. 2 is a side view (bc-projection) of the schematic ~ Le:S~IlLdtiOn of two smectite layers Fig.
l;
Fig. 3 is a schematic ~t~L~s~ ation of the charge distribution on the surf aces of sodium mont-morillonite clay platelets 6howing the di6tribution of positive and negative charges on the clay platelet 6urface6 a6 a re6ult of the natural di6position of the Na, Mg, Al, Si, and O atoms of the clay shown in Figs.
1 and 2;

-- 19 -- PATE~T App 28682/128~A
Fig. 4 i5 a graph plotting interlayer space for polyvinylpyrrolidone (PVP) :smectite clay complexes (intercalates) showing d(001) and d(002) spacings, in Ar.y~, (A), versus pe~ lLay~ of PVP sorbed, based on the dry weight of the smectite clay;
Fig. 5 is a graph plotting interlayer space for polyvinylalcohol (PVA) :smectite clay complexes (intercalates) showing d(001) spacing, in Ally~LL~ , between smectite clay platelets versus percentage of PVA sorbed, based on the dry weight of the smectite clay;
Fig. 6 is an x-ray diffraction pattern for a complex of PVP (weight average molecular weight of 10,000) :sodium montmorillonite clay, in Ang~LL , at a weight ratio of PVP:clay of 20:80;
Fig. 7 is an x-ray diffraction pattern for a complex of PVP (weight average molecular weight of 40,000) :sodium montmorillonite clay, in Any~,LL , at a weight ratio of PVP:clay of 20:80;
Fig. 8 is an x-ray diffraction pattern for a complex of PVA (weight average molecular weight of 15, 000) :sodium montmorillonite clay, in Al~y~LL , at a weight ratio of PVA:clay of 20:80;
Fig. 9 is an x-ray diffraction pattern for a complex of PVP:sodium montmorillonite clay, in Ang-stroms, at a weight ratio of PVP:clay of 20:80 (upper pattern), and an x-ray diffraction pattern for about 10096 sodium montmorillonite clay having a crystobalite impurity (lower pattern);
Fig. 10 is an x-ray diffraction pattern for a complex of PVP:sodium montmorillonite clay, in Ang-stroms, at a weight ratio of PVP:clay of 50:50 (upper pattern), and an x-ray diffraction pattern for about ~ 21~6196 - 2 0 - PATE~T APPL}CATIO~i ~8682/128~A
10096 sodium montmorillonite clay having a crystobalite impurity ( lower pattern);
Fig. 11 i5 an x-ray diffraction pattern for untreated sodium montmorillonite clay, in An~ L
Fig. 12 i6 a portion of an x-ray diffraction pattern for PVP:sodium montmorillonite clay, in Ang-stroms, at a PVP:clay ratio of 80:20, showing a PVP:clay complex peak or d(OOl) spacing of about 41 A;
Figs. 13 and 14 are x-ray diffraction 10 patterns, respectively, of wet and dry samples of Example #1;
Figs. 15 and 16 are x-ray diffraction patterns, respectively, of wet and dry samples of Example #ga; ~ ~
Figs. 17 and 18 are x-ray diffraction patterns, respectively, of wet and dry samples of Example ~gb;
Figs. 19 and 20 are x-ray diffraction patterns, respectively, of wet and dry samples of 20 Example ~lOd;
Figs. 21 and 22 are x-ray diffraction patterns, respectively, of wet and dry samples of Example #llc;
Figs. 23 and 24 are x-ray diffraction 25 pa~ L~ respectively, of wet and dry samples of Example #12a;
Figs. 25 and 26 are x-ray diffraction patterns, respectively, of wet and dry samples of Example #12b;
Figs. 27 and 28 are x-ray diffraction patterns, respectively, of wet and dry samples of Example ~12c; and ~ 2186196 - 21 -- PAT~NT AppT Tt"~---28 682 /128~A
Figs. 29 and 30 are x-ray diffraction patterns, respectively, of wet and dry samples of Examples #13a-d.
nRT~TT lZn r~r ~ ~ OF ~TTF ~ F.~
To form the intercalated and, optionally, exfoliated pesticides of the present invention, the layered material, e.g., the phyllosilicate, is acti-vated, i.e., swelled or intercalated, by water, an intercalant polymer, a water-m;c~;hl~ organic solvent, or mixture thereof, followed by sorption of an inter-calant pesticide . In accordance with a pref erred L of the present invention, the activated phyll~c;l;cate includes 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 pesticide to achieve sufficient intercalation, ~spc~c;Ally if the pesticide intercalate will be exfoliated. Preferably, the phyllosilicate include6 at lea6t about 4% by weight water before contact with the intercalant pe6ticide f or ef f icient intercalation .
~he amount of intercalant pesticide in contact with the phyllosilicate, ~cpec;Al ]y for efficient exfoliation, 6hould provide an intercalant pe6ticide/phyllosilicate weight ratio (ba6ed on the dry weight of the phyllosilicate) of at least about 1:20, preferably at least about 3:20, and more prefer-ably about 4-14:20, to provide efficient sorption and complexing (i.e., intercalation) of the intercalant ~ 21~61~6 -- 22 -- PA~ENr APPT Tr 28682/128~A
pesticide between the platelets of the layered materi-al, e.g., phyllosilicate. Intercalation of the intercalant pesticide, especially nonpolar intercalant pesticides, is facilitated by using an intercalant 5 polymer and water to activate the phyllosilicate.
The intercalant pesticides are introduced in the form of a solid or liguid composition (neat or agueous, with or without a polar or nonpolar organic solvent, e.g., an aliphatic llydrV~:OL~ , such as 10 heptane) having an intercalant pesticide concentration of at lea6t about 2%, preferably at least about 51, more preferably at least about 10%, and most prefera-bly at least about 50% to about 100% by weight inter-calant pesticide, ba6ed on the weight of the pesticide ' and carrier, for intercalant pesticide sorption. The intercalant pesticide can be added as a solid with the addition to the layered material/-intercalant pesticide blend of about 20% water, preferably at least about 30% water to about 5,000%
20 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 materi-25 al, is used when extruding or pug milling, so thatless water i8 60rbed by the intercalate, thereby necessitating less drying energy after intercalation.
The pesticide intercalants can be introduced into the spaces between every layer, nearly every layer, or at 30 least a precl~ ; n~nc.e of the layers of the layered material such that the platelet particles, if subse-guently exfoliated, are preferably pr~ i n:-ntly less than about 5 layers in thickness, more preferably, , ~. 21861q6 ; n~ntly about 1 or 2 layers in th; rknP~ ~ and most preferably, prP~ ;n~lntly single platelets.
Any swellable layered material that suffi-ciently sorbs the intercalant pesticide to increase the interlayer spacing between adjacent phyllosilicate platelets to at least about 10 A (when the phyllosili-cate is measured dry) can be used in the practice of this invention. Useful swellable layered materials include phyllosilicates, such as smectite clay miner-als , e. g., montmorillonite, particularly sodium montmorillonite, magnesium montmorillonite and/or calcium montmorillonite, nontronite, bP;~lP~ 1 ;te, 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 can be used in this invention provided they can be intercalated with the intercalant pesticides to expand their interlayer spacing to at least about 5 A, preferably at least about 10 A.
Preferred swellable layered materials are phyllo-silicates of the 2 :1 type having a negative charge on the layers ranging f rom about o . 15 to about O . 9 charges per formula unit and a ~ te number of exchangeable metal cations in the interlayer spaces.
Most preferred layered materials are smectite clay minerals such as montmorillonite, nontronite, bPitlPl 1 ite, volkonskoite, hectorite, saponite, sauconite, sobockite, stevensite, and svinfordite.

~ 21~619~

28682/128~A
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 .l~l Im;n~tion (i.e., 5 exfoliation~ takes place. The interlayer spacing is measured when the layered material is "air dry," i.e., 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 pref erred 10 clay materials generally include interlayer cations such as Li+ ~lithium), Na+, Ca+2 (calcium~, R+ (potas-sium), Mg+2, NH4+ ( ;l-m) ~ and the like, including mixtures thereof.
In accordance with a preferred _'; L of 15 the present invention, the phyllosilica~e is contacted with an aqueous solution of an intercalant polymer to provide a sufficient spacing between adjacent plate-lets to permit intercalation of polar and/or nonpolar pesticides. The intercalant polymer should be water 20 soluble (herein defined as sufficiently soluble 6uch that at least 0.1 gram of the polymer will dissolve per 100 grams of distilled water at 25OC). In accor-dance with a preferred ~omhollir L of the present invention, the intercalant polymer includes a func-25 tionality selected from the group consisting of acarbonyl, carboxyl, hydroxyl, amine, amide, ether, ester, sulfate, sulfonate, sulfinate, sulfamate, phosphate, rh-~srhnn~te~ rhosrhin~te~ or an aromatic ring to be sufficiently complexed or bound to the 30 platelet surfaces of the layered material. Such intercalant polymers have sufficient affinity for the phyl l ~ te platelets to provide suf f icient inter-layer spacing for exfoliation, e.g., ~bout 5 ~ to ~ 21861q~
- 25 - PATENr APPr.
28682/128~A
about 100 ~, preferably about 10 A to about 50 A, and to maintain att~ ~ to the surfaces of the plate-lets, without the need for coupling agents or spacing agents, such as the onium ion or silane coupling agents ~ closP~-.in the above-mentioned prior art.
Sorption of the intercalant polymer should be sufficient to achieve PYr~nc;~n of adjacent plate-lets of the layered material (when measured dry, i.-e., having a maximum of about 5% by weight water) to an interlayer spacing of at least about 5 A, preferably-a spacing of at least about 10 A, more preferably a spacing of at least about 20 A, and most preferably a spacing of about 30-45 A. To achieve intercalates that easily incorporate a nonpolar pesticide or that can be exfoliated easily using the preferred water-soluble polymer intercalants disclosed herein, such as polyvinylpyrrolidone, polyvinyl alcohol, and mixtures thereof, the weight ratio of intercalant polymer to layered material, preferably a water-swellable smec-tite clay such as sodium bentonite, in the interca-lating compos ition contacting the phyl los i 1 icate should be at least about 1:20, preferably at least about 1:12 to 1:10, more preferably at least about 1:4, and most preferably about 1:3 to about 1:2. It is preferred that the c~ lLL~tion of polymer, based on the total weight of intercalant polymer plus intercalant carrier (water plus any organic liquid solvent) is at least about 15% by weight, more prefer-ably at least about 20% by weight polymer, for example about 20%-30% to about 90% by weight polymer, based on the weight of polymer plus intercalant carrier (water plus any organic solvent) during intercalation.

~ ~ 2l86l96 In a~.uLd~ with a preferred Pmho~ t of the present invention, the combination of layered material and aqueous solution containing an inter-calant polymer includes at least about 4% by weight water, up to about 5000% 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 polymer to achieve suf f icient polymer intercalation. Preferably, the phyllosilicate ;nrlll~9P~ at least about 4% by weight water before contact with the polymer for Pff;~-;Pnt intercalation.
The amount of intercalant polymer in contact with the phyllosilicate for efficient exfoliation, should provide efficient sorption and complexing (intercala-tion) of the polymer between the platelets of the layered material, preferably about 16 to about 70 percent by weight intercalant polymer, based on the dry weight of the layered 6ilicate material.
The preferred intercalant polymers are water-soluble and are added in the form of a solid or liquid (neat or aqueous solution or dispersion, with or without a liquid organic solvent, e.g., alcohol) having an intercalant polymer concentration of at least about 2%, preferably at least about 5%, more preferably at least about 50% to about 100%, by weight intercalant polymer, based on the dry weight of the layered material, for intercalant polymer sorption.
The polymer can be added as a solid with the addition to the layered material/polymer blend of at least about 20% water, preferably at least about 30% water to about 5000% water or ~ore, based on the dry weight of the layered material, with or without another ~ 21 8~ 96 28682/128~A
solvent for the intercalant polymer, preferably about 30% to about 50% water, more preferably about 30% to about 40%. The intercalant polymer can be introduced into the spaces between every layer, nearly every 5 layer, or at least a prP~l~ ;nAn~P of the layers of the layered material such that the subsequently eYfoliated platelet particles are preferably, prP~ ;n~ntly less than about 5 layers in thickness, more preferably, prP~-;n~ntly about 1 or 2 layers in th;~ knP~, and 10 most preferably, ~LF' ;n~ntly single platelets.
The amount of intercalant polymer interca- --lated into the swellable layered materials useful in this invention, in order that nonpolar pesticide _ ' can intercalate in the layered material, and 15 such that the layered material can be easily exfoliat-ed or ~lPl~min;~ted into individual platelets, can vary substantially between about 10% and about 80%, based on the dry weight of the layered silicate material.
In the preferred P~l~o-l;r L6 of the invention, amounts 20 of intercalants polymers employed, with respect to the dry weight of layered material being intercalated, preferably range from about 8 grams of intercalant polymer/100 grams of layered material (dry basis), preferably at least about 10 grams of polymer/100 25 grams of layered material, to about 80 to about 90 grams intercalant polymer/100 grams of layered materi-al. More preferred amounts are from about 20 grams intercalant polymer/ 100 grams of layered material to about 60 grams intercalant polymer/100 grams of 30 layered material (dry basis).
The polymer intercalants are introduced into ( i . e ., sorbed within) the interlayer spaces of the layered material in one of two ways . In a pref erred ~ 2~86196 -- 28 - PATBNT APPLICAq!ION

method of intercalating, the layered material and an intercalant polymer or intercalant polymer/water solu-tion, or intercalant polymer, water and an organic solvent, are intimately mixed, e.g., by extrusion or pug milling. To achieve sufficient intercalation for exfoliation, the layered material/intercalant polymer blend contains at least about 8%, preferably at least about 10%, by weight intercalant polymer, based on the dry weight of the layered material. The intercalating carrier (preferably water, with or without an organic solvent) can be added by first solubilizing or dis-persing the intercalant polymer in the carrier, or the dry intercalant polymer and relatively dry phyllo-silicate (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 polymer. In every case, it has been found that 6urprising sorption and Y;nq of intercalant polymer between platelets is achieved at relatively low loadings of intercalating carrier, ~ peciAlly water, e.g., at lea6t about 4% by weight water, based on the dry weight of the phyllo-silicate. When intercalating the phyl l ~ i l 1 cate in slurry form (e.g., 900 pounds water, 100 pounds phyl l o~i 11 i cate, 25 pounds polymer) 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 (the phyllosilicate intercalate is easily separated from the int~rcalating composition).
3 0 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 polymer, either dry or in -~ .~

- 29 -- PATENT AP~LICATION

solution. Sorption of the intercalant polymer mole-cules can be performed by exposing the layered materi-al to dry or liquid intercalant polymer compositions containing at least about 2%, preferably at least 5 about 5%, by weight intercalant polymer, more prefera-bly at least about 50% intercalant polymer, based on the dry weight of the layered material. Sorption can be aided by t~ JOl:lUL'2 of the intercalating composition to heat, pressure, ultrasonic cavitation, or micro-10 waves.
In accordance with another method of inter-calating the intercalant polymer between the platelets of the layered material and exfoliating the interca-late, 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 a water-soluble intercalant polymer in a ratio sufficient to provide at least about 89G by weight, preferably at least about 10% by weight, intercalant 20 polymer, based on the dry weight of the layered material. The blend then preferably is extruded for faster intercation of the polymer with the layered material .
The preferred intercalant polymers are 25 water-soluble, such as polyvinylpyrrolidone (PVP) having a repeating structure (~) as follows:

~i 2~86196 -- 3 0 -- PATENT AppT.T
28 682 /128~A

CH~ C /
CH2--CH~
-- n, wherein n i8 a number from 2 to about 1500. The water-solubility of PVP can be adjusted according to (1) the degree of hydrolysis of the polyvinylpyrroli-done, and (2) by forming ~ metal salt of PVP, such as 5 sodium or potassium. PVP can be hydrolyzed to the structure ( I I ):
--CH--CH~--NH
(CHz)3 C~2H n (II) and the PVP, or copolymers of vinylpyrrolidone and a vinyl amide of ~y-amine butyric acid, can be interca-lated in the salt ~orm, e . g., sodium or potassium 10 polyvinylpyrrolidone polymers. Preferred PVP inter-~ 21~61~6 - 31 - PATENT App 28 682 /128~A
calant6, and the following PVP derivatives, have a weight average molecular weight in the range of about 210 to about lOO,OOO or more, more preferably about l,OOO to about 40,000.
Other suitable water-soluble vinyl polymers include poly (vinyl alcohol) --CH--CH~--OH
n The polyvinyl alcohols (PVA) function best when they are essentially fully hydrolyzed, e.g., 5% or less acetyl groups, preferably 196 or less residual acetyl groups. A lower molecular weight PVA flln~-ti~n~ best, e.g., a weight average molecular weight of about 2,000 to about 10,000, but higher molecular weight PVA also functions, e.g., up to about 100,000.
The polyacrylic acid polymers and copoly-mers, and partially or fully neutralized salts, e.g., metal salts, are also suitable, having ~onomer units:
--CH--CHz--COzH
and are commercially available as CARBOPOL resins from B. F. Goodrich and PRIMAL resins from Rohm & Haas.
Light cross-linking is acceptable, as long as water ~ .~
2 1 8~ 1 96 -- 32 -- PATENT AppT T~'~
28682/128~A
solubility i5 retained. Weight average molecular weights for the polyacrylic polymers and copolymers described above and below of about 10, 000 or less, e.g., about 200 to about 10,000, intercalate more 5 easily, but higher molecular weight polymers, up to about 100,000 or more, also function.
other water-601uble derivatives of, and substituted, polyacrylic acids also are useful as intercalant polymers in accordance with the present 10 invention, such as poly(methacrylic acid) (PMAA), having a repeating monomeric structure:
_ --C CH~--- n Similar water-soluble polymers and copoly-mers that are suitable in accordance with the present 15 invention include poly(methacrylamide), or PMAAm, having a general repeating monomeric LLLU~ LULe C~
I

NH~ n 2~ 86~ 96 - 33 - PATENT APPr~Tf'~-Poly(N,N-dimethylacrylamide), having the gener-al re-peating monomeric structure:

T~
N(CH3~2 n .

Poly (N-isopropylacrylamide), or PIPAAm, 5 having the general repeating monomeric structure:
-- 'H--CH2--:D
~H
HC~CH~)~
- n .

Poly(N-acetamidoacrylamide) having a general repeating ~- ic nL~ ,Lu~a:

. ~. 2~86~96 - 34 - PATENl~ APPLICATIo~
28682/128~A
--CH--CHZ--~o "H

:o ~HZ
- n and poly (N-AC'etm; ~' ~hacrylamide) having a genera repeating monomeric structure:
~H, ,--CH2 CD
~IH

_o ~H~
- n 5 Water-soluble copolymers; nr~ ; n~ any one or more of the above-described acrylic polymers also are useful in accordance with the principles of the present invention, ;ncll~l;n~ the acrylic interpolymers of l .~
2 1 861 9~
-- 3 5 -- PATE~r APPLICAq'ION
28682/128~A
polyacrylic acid and poly (methacrylic acid), poly-acrylic acid with poly- (methacrylamide), and poly-acrylic acid with methacrylic acid.
Other 6uitable water-soluble polymers in-5 clude polyvinyloxazolidone (PVO) and polyvinylmethyl-oxazolidone (PVMO), having the general repeating monomeric structures:

,;~! \c ~~
PVO: R=H
P'~110: R=CH3 Also suitable are poly~,~y~lu~ylene-poly.,.~y~:~l.ylene block polymers that conform to the formulas:
HO CHCH~O (CH~CH~O~y CHCH O H
CH3 x CH3 lo and .
~8~19 - 3 6 -- ~A~ENT APPLICA'rION
28682tl28~A
HO jHCH20 ~CH2CH20~y CH2CHO H

X ~
wherein x and z are each an integer in the range of about 4 to about 30, and y i6 an integer in the range of about 4 to about 100, for example Meroxapol 105, Il_Lul~a~uOl 108, Il_L~ E,01 171, Meroxapol 172, Merox~pol 174, Il~Lu~Lapol 178, Merpxapol 251, Meroxapol 252, Neroxapol 254, II-LU~ O1 255, Meroxapol 258, Meroxapol 311, I~_LU~PO1 312, and Meroxapol 314.
Other suitable water-soluble/water-dispers-10 ible intercalant polymers include, but are not limited to, polyacrylamide and copolymers of acrylamide, acrylamide/sodium acrylate copolymer, acrylate/-acrylamide copolymer, acrylate/ammonium methacrylate copolymer, acrylate~ r~tt~n~a~rylamide copolymers, 15 acrylic/acrylate copolymers, adipic acid/dimethyl-amino~lydLu,.y~luuyl diethylenetriamine copolymer, ammonium acrylate copolymers, i llm styrene/-acrylate copolymers, ammonium vinyl acetate/acrylate copolymers, AMP acrylate/~i~t.-ett n~acrylamide copoly-20 mers, AMPD acrylate/(li~ceton~rylamide copolymers,butyl benzoic acid/phthalic anhydride/trimethyl-olethane copolymer, cornstarch/acrylamide/sodium acrylate copolymer, diethylene glycol~min~/epichloro-hydrin/piperazine copolymer, tl~d~c~n~lioic acid/-25 cetearyl alcohol/glycol copolymers, ethylene/vinylalcohol copolymer, ethyl ester of polyethyl~nimin~
~such as llydLu~-yt:Lhyl/PEI-1000 and hydroxyethyl PEI-.
21861~6 28682/128~A
1500), isopropyl e6ter of PVM/MA copolymer, r~ min~
f- rr~ hyde resin, methacryloyl ethyl betaine/meth-acrylate copolymers, methoYy PEG-22/dodecyl glycol copolymer, oct~flPc~nP/maleic anhydride copolymer, 5 octylacrylamide/acrylate/butyl ~mi noethyl methacrylate copolymers, octyl-acrylamide/acrylate copolymers, PEG/dodecyl glycol co-polymers, polyethyl~-n~; m; n~
(such as PEI-7, PEI-15, PEI-30, PEI-45, PEI-275, PEI-700, PEI-1000, PEI-1500, and PEI-2500), phthalic 10 anhydride/glycerin/glycidyl decanoate copolymer, metal salts of acrylic and polyacrylic acid, polyaminopropyl biguanide, polymeric quaternary: ;llm salts (such as polyquaternium-l, polyquaternium-2, poly-quatern-ium-4, polyquaternium-5, polyquaternium-6, poly-15 quaternium-7, polyquaternium-8, polyquaternium-9, poly-quaternium-10, polyquaternium-11, polyquaternium-12, polyquaternium-13, polyquaternium-14, and poly-quaternium-15), polyvinyl imidazolinium acetate, potassium polyacrylate, sodium polyacrylate, metal 20 salts of PVM/MA copolymers, (e.g., Li, R, Na, Ru, Ce salts), PVP/eicosene copolymers, PVP/ethyl methacry-late/methacrylic acid copolymer, PVP/hl~Y ~ cF~n~
copolymer, PVP/VA copolymer, PVP/vinyl acetate/-itaconic acid copolymer, sodium acrylate/vinyl alcohol 25 copolymers, sodium C4-C12 and other metal salts of olefin/maleic acid copolymers, sodium polymethacryl-ate, sodium polystyrene sulfonate, sodium styrene/-acrylate/PEG-10 dimaleate copolymer, water-soluble esters and ethers of cellulose, sodium styrene/PEG-10 30 maleate/nonoYynol-10 maleate/acrylate copolymer,~
starch/acrylate/acrylamide copolymers, styrene/-;~crylamide copolymer, styrene/acrylate/ammonium methacrylate copolymer, styrene/maleic anhydride .
2~861~6 - 3 8 - PATENl APPr.
28682/128~A
copolymer, styrene/PVO copolymer, sucrose benzoate/-sucrose acetate iso~u~yLc~l_e/butyl benzyl phthalate copolymer, sucrose benzoate/sucrose acetate i50-butyrate/butyl benzylphthalate/methyl methacrylate copolymer, urea/-formaldehyde prepolymers, urea/r-lAmin~/formaldehyde prepolymers, vinyl ace-tate/crotonic acid copolymers, vinyl alcohol copoly-mer6, and mixtures thereof. Other water-soluble polymeric polyols and polyhydric alcohols, such as polysaccharides, also are suitable as polymer inter-calants .
After contact between the layered material and water or the aqueous solution of intercalant polymer and/or water-miscible organic solvent, the resulting composition typically is a paste. An inter-calant pesticide, either neat or in solution, then is added to the paste. The water and intercalant polymer activated the layered material such that the inter-calant pesticide now intercalates between surfaces of the layered material. The pesticide is added as a liquid or as a solid to the activated layered materi-al, and the resulting mixture typically is extruded to facilitate intercalation of the intercalant pesticide.
Alternatively, the layered material, water, optional polymer and organic solvent, and intercalant pesticide all can be admixed, then extruded.
The amount o~ intercalant pesticide interca-lated into the activated layered material varies substantially between about O . 01% and about 40~6, and preferably between about 0.196 and 309c, based on the dry weight of the layered silicate material. The amount of intercalated pesticide generally is an amount sufficient for the pesticide to perform its - 3 9 -- PATENT APPLIcATION
28682/128~A
intended function. ~Iowever, high percentages of pesticide can be intercalated to provide a cullc~ LL~t-ed intercalated pesticide that is subsequently diluted with a liquid or solid carrier to provide a pesticide 5 composition. The amount of intercalant pesticide intercalated into the layered material, therefore, can be substantially greater than the maximum of about 10%
by weight pesticide applied to r~ 1 r.i n~d clays .
In preferred ~mho~ s of the invention, 10 the amount of intercalant pesticides employed, with respect to the dry weight of layered material being intercalated, ranges from about 0.1 grams of inter-calant pesticide: 100 grams of layered material (dry basis), preferably at least about 1 gram of inter-15 calant pesticide: 100 grams of layered material toabout 40 grams intercalant pesticide: 100 grams of layered material. More preferred amounts are from about 5 grams intercalant pe6ticide/100 grams of layered material to about 30 grams intercalant pesti-20 cide/100 grams of layered material (dry basis). Toachieve sufficient intercalation for exfoliation, the layered material/ intercalant pesticide blend contains at least about 8% by weight, and preferably at least about 10%, by weight intercalant pesticide, based on 25 the dry weight of the layered material.
The intercalant pesticides are introduced into (i.e., sorbed within) the interlayer spaces of the layered material in one of two ways. In a pre-ferred method, the intercalant pesticide is dis~:olved 30 in a solvent, and the intercalant pesticide solution is admixed with the layered material either bef ore or after the layered material has been activated by contact with water or an aqueous solution of an ~ . ~
~1~61q6 28682/128~A
intercalant polymer and/or water-miscible organic solvent. In an alternative method, the pesticide is added in a neat form to the activated layered materi-al. The resulting miYture is extruded or pug milled 5 to form an intercalated compo-sition comprising the activated layered material and an intercalant pesti-cide. The resulting mixture typically is a paste that, after pesticide intercalation, is dried, then p-~lleti7ed to form a pesticide composition.
The intercalant pesticide carrier ( i . e ., water, an organic solvent, or a mixture thereof ) can be added by first sol~lhi1i~inJ or dispersing the intercalant pesticide in the carrier, or a dry inter-calant pesticide and relatively dry phyllosilicate 15 ~preferably containing at least about 4~6 by weight water) can be blended and the intercalating carrier added to the blend, or to the phyllosilicate prior to adding the dry intercalant pesticide. In every case, it has been found that surprising sorption and 20 complexing of intercalant pesticide between platelets is achieved at relatively low loadings of intercalat-ing carrier, ~~cp~ lly water, e.g., at least about 49~
by weight water, based on the dry weight of the phyllosilicate. When intercalating the phyllosilicate 25 in slurry form, 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 30 composition).
Alternatively, the intercalating carrier can be added directly to the phyllosilicate prior to adding the intercalant pesticide, either dry or in 21 861 ~6 28682/128~A
solution. Sorption of the intercalant pesticide mole-cules can be performed by exposing the layered materi-al to dry or liquid intercalant pesticides in the intercalating composition containing at least about 5 0.01%, preferably at least about 0.1%, more preferably - at least about 1%, intercalant pesticide, ba6ed on the dry weight of the layered material. Sorption can be aided by t~ 0'-UL~ of the intercalating composition to heat, ~ saur ~=, ultrasonic cavitation, or microwaves.
In accordance with another method of inter-calating the intercalant pesticide between the plate-lets of the layered material, and optionally exfoliat-ing the intercalate, the layered material, containing at least about 4%, and preferably about 10% to about 15%, by weight water, i6 blended with an intercalant pesticide in a ratio sufficient to provide at lea6t ~bout 8% by weight, preferably at least about 10% by weight intercalant pesticide, based on the dry weight of the layered material. The blend then preferably is extruded for faster intercalation of the intercalant pesticide with the layered material.
An intercalant pesticide having a polar moiety has an affinity for the phyllosilicate 80 that it is sorbed between, and is maintained associated with the surfaces of the silicate platelets, in the interlayer spaces, and after exfoliation. Pesticides lacking a polar moiety can be intercalated into a layered material that previously has been activated with water and a water-soluble polymer.
In accordance with the present invention, the intercalant pesticide preferably includes a polar moiety, like a carbonyl functionality, to be suffi-ciently bound, as theorised herein, by a r-~h~niF~

'--' 2l~6lq6 - 42 - PATEN~r APPLICATION
28682/128~A
8-~l ertecl from the group consisting of ionic complex-ing, ele~ ~L~.,.Latic complexing, chelation, llyd~
bonding, dipole/dipole interaction, Van Der Waal6 forces, and any combination thereof. Such bonding, via the metal cations of the phyllosilicate sharing electrons with ele~LL~ ytlLive atoms of a polar moiety of one intercalant pesticide molecule or of two adjacent intercalant pesticide molecules, to an inner surface of the phyllosilicate platelets provides adherence between the polar moiety and the platelet inner surfaces of the layered material. Such inter-calant pesticides 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. In pesticides lacking a polar moiety, the water-soluble polymer separates the platelets of the layered material a sufficient amount to allow the pesticides to inter~alate between adja-cent layers. The pesticide, either containing or lacking a polar moiety, displaces water and the water-soluble polymer from the space between adjacent layers of the layered material.
As shown in Figs. 1-3, the disposition of surface Na+ ions with respect to the disposition of O, Mg, si, and Al atoms, and the natural clay substi-tution of Mg+2 cations for Al+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 alternatin~ positive to negative surface charge over spans of the clay platelets surfaces, and on the clay platelet surfaces in the interlayer l . ~
21 861 q ~
~ 43 - PATENT APPT Tr~
28 682 /128~.A
spacing, provide for excellent dipole-dipole attrac-tion of pesticide molecules having a polar moiety for intercalation of the clay, and, after optional exfoli-ation, for bonding of such polar pesticide molecules 5 on the platelet 6urfaces.
In accordance with an important feature of thepresent invention, the intercalatedphyllo~;l;cate can be manufactured in a cul.c~ L<lted form, e.g., up to 40%, preferably 1-30%, intercalant pesticide, by weight, and 10-90%, preferably 20-80%, intercalated phyllosilicate, by weight, and can be dispersed in an organic solvent and exfoliated, before or after addition to the solvent, to a desired platelet load-ing .
Pesticides useful in the present invention include ; nl:u~Ct; ~; fl~ herbicides, acaricides, growth regulators, rodenticides, defoliants, fungicides, larvacides, nematocides, repellents, ;~nd other com-pounds capable of r~r~llinq, mitigating, or destroying 20 undesirable and objectionable plants and animals.
Preferred pesticides are organic _ '- having at least one polar moiety. Polarity of the moiety results from two adjacent atoms that are covalently bonded, wherein a first atom having a low electronega-25 tivity is bonded to a second atom having a higherele~:LLulleu,ativity. The difference in el~uLLu.leu,a-tivity between the two atoms (e.g., preferably at least about 0. 5 electronegatiYity units) creates a charge differential between the first and second 30 atoms, i.e., polarity. The first atom of lower electronegativity generally has an electronegativity of at least 2, the second atom of higher electro-negativity has an ele~ LLulleu,-ltivity preferably at '--' 2l86l96 least 0.5 ele.;~Lu~ley~ivity units greater than the first atom, and typically is an atom such as oxygen, sulfur, or nitrogen.
The polar moiety of the organic pesticide 5 ~ _ ' often is a carbonyl moiety, such as in a carboxylic acid or salt thereof, an ester, an amide, an anhydride, a ketone, or an aldehyde. However, the polar moiety also can be cyano, nitro, thiocarbamate, amino, carbamic, phosphate, thiorhns~h~te, sulfoxide, 10 carb~n~;mi-l~, urea, sulfone, phosphorothioate, phos-phorodithioate, thiourea, dithiocarbamate, phos-phoramidodi-thioate, methylsulfonyl, rh-~srht~n;te, sulfamide, phosphoramide, sulfonate, dithio~ -IL,ul~ate, hydroxyl, sulfate, sulfinate, sulfamate, or phos-15 phinate moieties, for example. The polar moiety alsocan be other moieties containing a combination of 6ulfur and oxygen atoms, or a combination of phospho-rus and oxygen atoms.
Organic pesticide ~ ~_ '- containing one 20 or more polar moieties are particularly suitable for use as intercalant pesticides in accordance with the present invention. Eowever, pesticides lacking a polar group also can be used in the intercalant pesticide when an intercalant polymer i5 used to 25 activate the layered material. The following are nonlimiting examples of pesticides useful in the present invention. The li~ts are intended to set forth examples of useful pesticides and are not intended to limit the pesticides that can be used in 3 0 the present inve~tion .

.~. 2186196 - 45 - PATENT aPPi-JICATION
28682/128~A
FUNGICI~ES
Allyl alcohol, anilazine, tr;A~iir-nnl, benomyl, benquinox, bunema, captafol, captan, carben-dazim, carboxin, chinosol, chloroneb, çhlorothalonil, ~ - 5 cyclnh~Y;m;d~ dazomet, dicloran, dichlofluanid, dichlone, dimethirimol, dinocap, manzeb, dithianon, dodemorph, dodine, drazoxolon, edinfenphos, finAminnsll1f, fPn~rAn;l, fentiazon, ferbam, folpet, fongarid, guazatine, hymexazol, iprodione, kasugamycin, maneb, MEMC, methylthiophenate, metiram, nabam, neo-asozin, _-phenylphenol, Pi~5A, oxycarboxin, parinol, PCNB, phosethyl, piperalin, polyoxin, pro-cymidone, propineb, propazine, propionic acid, prothiocarb, pyracarbolid, pyrazophos, ~hiAh-~n~ ole, thiophanate, thiram, tolylfluanid, triadimefon, tridemorph, triforine, triphenyltin acetate, validamycin A, vinclozolin, vondozeb, zineb, chloranil, ziram, 8-quinolinol, CDEC, metam, glyodin, 2,6-bis[dimethylaminomethyl]cyclnhPY~nnn-~, h~Y~nhloro-acetone, bromoacetyl bromide, picloram, benalaxyl, blasticidin S, bupirimate, buthiobate, ~-h;n~ Lhi-onate, chlozolinate, ~:y n; 1, ~:yj~u-,uilazole, dithianon, ethirimol, etridazole, fenarimol, fenpiclonil, fenpropidin, fenpropimorph, fentin, 25 flusilazole, flutriafol, flutolanl, fuberidazole, furalaxyl, imazalil, imibenconazole, iprnh~nrh~nc:, isoprothiolane, mancozeb, mepronil, methfuroxam, metsulfovax, myclobutanil, nuarimol, ofurace, oYadixyl, polyoxin B, polyoxin D, prochloraz, 30 procymidone, propiconazole, pyroquilon, quintozene, t~h~ An~70le, tetraconazole, triarimol, tricyclazole, triforine, and mixtures thereof, and in mixture with .
~1 861 96 - 46 - PATENr A~PLICA~ION
28682/128~A
other pesticides. Salts and esters of these fungi-cides also can be used as the pesticide.
TrF~RI~Tn~A
Acifluorfen, alachlor, alanap, alloxydim, 5 ametryn, amitrol, asulam, atrazine, azide, barban, benazolin, benefin, bensulide, bentazone, benthiocarb, benzoylprop, benzthiazuron, bifenox, acetochlor, acrolein, benazolin, buthidazole, all itlnrhlnr, bL ~ bromofenoxin, bromoxyni1, butach1or, 10 butralin, buturon, butylate, chlometoxynil, chlor-amben, chlor~L, vn, chlorfenprop, chloridazon, chlorotoluron, chloroxuron, chlorpropham, chlor-thiamid, CNP, crotoxyphos, cycloate, cyprazine, 2, 4-D, dalapon, 2,4-DB, DCPA, 2,4-DEP, ~ ';rhAm, 2,4-DP, 15 .1~ ~Lyll, diallate, dicamba, dichlobenil, dichlor-prop, diethatyl, difenoxuron, diclofop, d;-- - nn, dinitramine, dinoseb, dinoterb, d; ph_nAmi~, dipropetryn, diquat, diuron, endothall, erbon, ethofumesate, fenac, fenuron, flamprop, fluchloralin, 20 EPTC, pentachlorophenol, fl--~ LULUII, fluorodifen, flurecol, glyphosate, glyphosine, h.~YA7;nnn-~, ioxynil, isopropalin, is-~pLvLuL~, karbutilate, lenacil, linuron, MCPA, MCPB, mecoprop, medinoterb, methazole, meth~LoLLylle~ metobromuron, metolachlor, metoxuron, 25 metribuzin, molinate, monalide, 1 ;m-ron, monuron, naptalam, neburon, nitralin, nitrofen, norea, norflurazon, oryzalin, oxadiazon, paraquat, pebulate, p_nnY~l in, perfluidone, phenisopham, rh~ ~-I;rhAm~
picloram, procyazine, profluralin, prometon, 30 yL, ~Ly-" pronamide, propachlor, propanil, propazine, propham, secbumeton, siduron, silvex, simazine, swep, 2,4,5-T, 2,3,6-TBA, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutol, terbutryn, tetrafluoron, triallate, trietazine, trifluralin, vernolate, l-naphthaleneacetic acid, N-m-tolylphthalamic acid, 5 ethyl-l-naphthalene acetate, chloroacetic acid, trichloroacetic 2cid, p-chlv~ n~ l;c acid, dimethyl-amino-2,3,5-triio~lnh~n7Qate, 2-naphthoxyacetic acid, phenoxyacetic acid, 2-phen-,xy~L~,~ionic acid, o-chloro-phenoxy acetic acid, p-chlorophenoxy acetic acid, 10 MCPA, silvex, MCPB, p-bromophenoxy acetic acid, dimethylamino-4[2,4-dichlorophenoxy]butryate, 3-indolebutyric acid, 3-indoleacetic acid, 3-indole-propionic acid, gibberellic acid, N,N-dimethyl-8l~ncinAmic acid, 2-furanacrylic acid, endothal, 1-15 naphthaleneacetamide, CDAA, N-methyl-N-l-naphthyl-acetamide, N-l-naphthyl an~Am;~ll" 2-[3-chloro-phenoxy]propionamide, noruron, 1inuron, siduron, metobromuron, terbacil, chloroxuron, aminotriazole, cyanazine, chlorflurenol, chlorsulfuron, cyanazine, 20 cyometrinil, 3,6-dichloropicolinic acid, dichlofop, difenzoquat, ~;ph~nAmid, ethaflualin, ethepon, flurazole, flurenol, fluridone, fosamine, isouron, mefluidide, 1, 8-naphtha1ic anhydride, napropamide, pyrazon, thoibencarb, anilazine, diphenatrile, N-[2,4-25 .dichlorophenoxyl)acetyl-DL-methionine, daminozide, pyrazon, ethoxyquin, propham, EPTC, S-carboxymethyl-N,N-dimethyldicarbamate, rhnsrhAn, merphos, ethephon, tricamba, amiben, MCPD, glufosinate, indole-3-butyric acid, ,B-naphthoxyacetic acid, triclopyr, 9-undecylenic 30 acid, oxyf1urofen, dinitrocresol, flurtamone, diflufenican, difunon, fomesafen, clethodim, sethoxydim, haloxyfop, tralkoxydim, fenoxaprop, fluazifop, phaseolotoxin, rhizobitoxine, barban, ~ .~
21861~6 - 48 - PATENT APP~ICATION

ethephon, tetcyclacis, mepiquat chloride, ancymidol, uniconzaole, paclobutrazol, diquatop, p~n~ halin, karbutilate, asulam, clopyralid, flULUlSy~yL, chlor-imuron, chlorsulfuron, metsulfuron, buthidazole, 5 ;r~ thabenz, imazapyr, imazaquin, imazethapry, jC:OYAh~n~ cinmethylin, ethorl - te, and mixtures thereof, and in mixture with other pesticides.
Several of the herbicides listed above are acid ' . In addition to the acid form of such 10 herbicides, esters (e.g., esters derived from Cl-Cl2 alcohols) and salts (e.g., amine, potassium, lithium, and 60dium salts) of these herbicides can be used as the intercalant pesticide.

Acephate, aldicarb, aldoxycarb, aldrin, d-trans allethrin, allyxycarb, aminocarb, amitraz, ~7;nrhoc, azinphos, azocyclotin, azothoate, bendio-carb, benzomate, binapacryl, bomyl, BPMC, L~L. ,~c, bromophos-ethyl, bLI ~L-,~ylate, butacarb, buto-20 carboxim, chlordane, chlordecone, heptachlor, lindane, methoxychlor, toxaphene, butoxicarboxim, carbaryl, carbofuran, carbophenothion, cartap, chloridimeform, chlorfenethol, chlorfenvinphos, chlu rhoc~ chloro-benzilate, chloropropylate, chlorphoxim, chlorpyrifos, 25 chlorthiophos, coumaphos, CPMC, crufomate, cryolite, cyanofenphos, cyanophos, cyhexatin, cypermethrin, cythioate, DDT, DDVP, demeton, demeton-S-methyl, dialifor, diazinon, dicofol, dicrotophos, dieldrin, dienochlor, diflubenzuron, dimefox, dimethoate, 30 dimethrin, dinobuton, dioxacarb, dioxathion, disulfoton, DNOC, d-phenothrin, ~n(~c-5~-1 fan, enfrin, 218619~
- 49 - PA~ENq' AppT-EPN, ethiofencarb, ethion, ethoate, ethoprop, etrimf 05, f amphur, f enbutatin-oxide, f en i troth ion, f enson, f ensu l f oth i on, f enthion, f enva lerate, f onof 05, formetanate hydrochloride, formothion, fosthietan, 5 1Iydr u~rc:lle, isofenphos, isoxathion, isothioate, malathion, mecarbam, mecarphon, menazon, meobal, mephosfolan, mercaptodimethur, methamidophos, methidathion, methomyl, methoprene, MIPC, mirex, r - uLophos, MTMC, naled, nicotine, omethoate, lO oxamyl, oxydemeton-methyl, oxydisulf oton, parathion, permethrin, phenthoate, phorate, rhns~1 nno ~ phosmet, rhnSrh~mirlnn, phoxim, pirimicarb, pirimiphos, plifenate, profenofos, promecarb, propargite, propet~P~rhns~ propoxur, prothiophos, prothoate, 15 qllin;-lrhns, resmethrin, ronnel, ryania, salithion, schradan, sulfotepp, sulprofo6, t- ,hc~, TEPP, terbufos, tetrachlorvinphos, tetradifon, tetramethrin, tetrasul, thiocyclam-hydrogenoxalate, thi, ton, thio-quinox, triazophos, trichloronate, trichloron, vamido-20 thion, melvinphos, TEPP, trichlorofon, 0,0-dimethyl phosphorochloriodothioate, methyl parathion, demeton 0, dicapthon, 0,0-diethylpho~rhnrochloridothioate, propham, mat a c i l, m [ 1- ethy lpropy l ] pheny lmethy l -carbamate & m[l-ethylpropyl]phenylmethylcarbamate 25 (mixture), pyrethrum, benzyl thiocyanate, rotenone, eugenol, and mixtures thereof, and in mixture with other pesticides. Salts and esters of these insecti-cides also can be used as the intercalant pesticide.

~' 2~86i9~
~ 50 - PATENT AppT Tr 28682/128~A
MTI~-'T~'T.T.~-NI;~017~ PESTICIDES
Aminozide, ancymidol, anthraquinone, brodi-facoum, bromadiolone, butoxy polypropylene glycol, carbon tetrachloride, chlof lurecol -methyl ester, 5 chlormequat chloride, chlorophacinone, chloropicrin, chlorphonium, chlonitralid, co~ ~hl~r, coumafuryl, crimidine, cyoxmetril, deet, ~ costerol hydrochlo-ride, dibutyl phthalate, ethyl h~Y~n-~rl;ol, dichlo-fenthion, difenacoum, dikegulac 60dium, diphenylamine, 10 ethPrhr~n~, fenamiphos, fluoro~ et lmi~1~, glyoxime, gossyplure, heliotropin acetal, kinoprene, maleic hydrazine, mepiquat-chloride, ~ hyde, metam-sodium, naphthalene acetamide, l-naphthaleneacetic acid, nitrapyrin, pyriminal, scillirosid, sesamex, 15 sulfoxide, trifenmorph, triprene, warfarin, and mixtures thereof, and in mixture with other pesti-- - cides. Salts and esters of these pesticides also can be used as the intercalant pesticide.
In accordance with another r~rhO~liT L of the 20 present invention, the intercalates can be exfoliated, then used as a pesticide or a component in a pesticide composition, or dispersed in a solvent or carrier to provide a viscous or thixotropic pesticide composi-tion. In either case, the pesticide composition can 25 include various optional components and additives commonly employed in pesticide compositions. Such optional components include fillers, wetting agents, synergists, colorants, dispersants, emulsifiers, anti-caking agents, defoamers, dedusting agents, sequester-30 ing agents, coupling agents, water-softening agents, and the like. These optional ~ -ntS, and appro-. ~ 21861~6 - 51 - PATl2NT APPLICATIO~
- 28682/128~A
priate amounts, are well known to those skilled in the art .
The amount of intercalated and/or exfoliated layered material included in a liquid carrier or 5 solvent to form viscous compositions or thixotropic suitable to deliver the carrier-dis601ved or carrier-dispersed pesticide, can vary widely r~PrPn~;n~ on the intended use and desired viscosity of the pesticide composition. For example, relatively high amounts of intercalate, i.e., about 1096 to about 30% by weight of the total composition, are used to form solvent gels having exL~ ?Iy high viscosities, e.g., 5,000 to 5,000,00D centipoise (cps). Extremely high viscosi-ties, however, also can be achieved with a relatively small concentration of intercalates and/or exfoliates thereof, e.g., 0.1% to 5% by weight, by adjusting the pEI of the composition to about 0 to about 6 or about 10 to about 14 and/or by heatiny the composition above room temperature, e.g., in the range of about 25~C to about 200~C, preferably about 75~C to about 100~C.
In accordance with an important f eature of the present invention, compositions of the present invention containing an intercalate and/or exfoliate, and a solvent or carrier, can be manufactured in a concentrated form, e.g., as a master gel having about 10 to about 90%, preferably about 20 to about 80%, intercalate and/or exfoliated platelets of layered material and about 10 to about 90%, preferably about 20 to about 80%, carrier or solvent. The master gel can be diluted and mixed with additional carrier or solvent to reduce the viscosity of the composition to a desired level, or to reduce the pesticide concentra-tion to an efficacious and safe level for application.

28682/~28~1A
Intercalate or platelet particle loadings in the solvent or carrier are within the range of about 0. 01% to about 40% by weight, preferably about 0. 05%
to about 20%, more preferably about 0.5% to about 10%
5 of the total weight of the composition to signif i-cantly increase the viscosity of the composition. In general, the amount of intercalate and/or platelet particles incorporated into the carrier or solvent is less than about 30% by weight of the total composi-10 tion, and preferably from about O . 01% to about 20% byweight of the composition, more preferably from about 0. 01% to about 10% by weight of the composition.
The intercalates, and/or eYfoliates thereof, are mixed with a carrier or solvent to produce viscous 15 compositions including one or more pesticide com-pounds, 6uch as an insecticide, dissolved or di6persed in the carrier or solvent. In accordance with an important f eature of the present invention, a wide variety of pesticide compounds can be incorporated 20 into a stable composition of the present invention.
Such active compositions include insecticides, herbi-eides, and fungicides that act upon contact with the insect, plant, or fungus to topically destroy the pest, or are absorbed or ingested by the pest to 25 systemically destroy the pest.
In accordance with another important feature of the present invention, a second pesticide or an optional -n~nt can be solubilized in a composition of the present invention or can be h~ cly 30 dispersed throughout the composition as an in601uble, particulate material. In either case, pesticide compositions of the present inven~ion are resistant to composition separation and effectively apply the ~ .~
~18G196 - 53 - PATENl APPLICATION
28682/128~A
pesticide c _ ~ to the desired area of application.
If required for stability, a surfactant can be includ-ed in the composition, such as any disclosed in T~l~ghl;n et al. U.S. Pat. No. 3,929,678, hereby 5 incorporated by ref erence . In general, the pesticide compositions of the present invention d LL,,te essentially no phase separation when the second pesticide L ~lu~-d and/or optional components are either solubilized or dispersed as an insoluble 10 material in the compositions.
Therefore, in accordance with an important feature of the present invention, the stable interca-lated pesticide composition can include any of the generally known pesticides as the second pe6ticide, 15 often in the form of a finely divided solid. In general, the amount of the second pesticide ~u~ld in the composition can range from 0%, preferably about 0.01%, to about 40%, and preferably from 0.1% to about 30%, by weight of the total composition. The amount 20 of surfactant can range from 0%, preferably about 0.01%, to about 15% by weight of the total composi-tion .
An optional exfoliation of the intercalated layered material typically rl~ nin;~tes at least about 25 90% by weight of the intercalated material. Exfolia-tion provides a more viscous composition when the intercalated pesticide is homogeneously dispersed in a carrier or solvent. Some intercalates require a shear rate that is greater than about 10 sec~1 for 30 relatively thorough exfoliation. The upper limit for the shear rate is not critical . In pref erred embodi-ments of the invention, when shear is employed for exfoliation, the shear rate is greater than about 10 ~ 2 ' 86 1 q6 28682/128~
sec~1 to about 20,000 sec~1, and in more preferred embodiments, the shear rate is about 100 sec~1 to about 10,000 sec~1. Such intercalates exfoliate naturally or by heating, or by applying ~les~uL~, e.g., 0.5 to 60 5 atmospheres above standard ~ I'~riC ~L~S~UL~:: with or without heating.
When shear is employed for exfoliation, any known method for applying a shear to the intercalant/-carrier composition can be used. The shearing action 10 can be provided by any appropriate method, as for example by mechanical means, by thermal shock, by pressure alteration, or by ultrasound, all of which are known in the art. In particularly useful proce-dures, the composition is sheared by r ~ n i ~ l means 15 in which the intercalate, with or without the carrier or solvent, is sheared by stirrers, Banbury D-type mixers, BrabenderD-type mixers, injection molding machines, long continuous mixers, extruders, and similar mechanical means. Another procedure employs 20 thermal shock in which shearing is achieved by alter-natively raising or lowering the temperature of the composition causing thermal expansions and resulting in internal stresses which cause shear. In still other ~)L~/C~:dULeS, shear is achieved by sudden ~Les~uL~:
25 changes in pressure alteration methods, by ultrasonic techniques in which cavitation or resonant vibrations cause portions of the composition to vibrate or to be excited at different phases and thus subjected to shear. These methods of shearing are merely represen-30 tative of useful methods, and any method known in theart for shearing intercalates may be used.
Shearing can be achieved by introducing the activated layered material and intercalant pesticide, ~ .~

Z86tZ/128~A
or mixture thereof, at one end of an extruder (single or double screw) and receiving the sheared material at the other end of the extruder. The temperature of the layered material/intercalant pesticide composition, 5 the length of the extruder, res idence time of the composition in the extruder and the design of the extruder (e.g., single screw, twin screw, number of flights per unit length, channel depth, flight clear-ance, mixing zone) are several variables which control 10 the amount of shear to be applied for exfoliation.
Alternatively, the layered material can be activated and intercalated by introducing the layered material, water, water-soluble polymer, and intercalant pesti-cide, or a mixture thereof, at one end of the 15 extruder.
Exfoliation is sufficiently thorough to provide at least about 80%, preferably at least about 85%, more preferably at least about 909~, and most preferably at least about 95% by weight ~PlAm;nAtion Z0 of the layers to form individual platelet particles that can be substantially homogeneously dispersed in the carrier or solvent. As formed by this process, the platelet particles dispersed in the carrier or solvent have the thickness of the individual layers 25 plus one to five monolayer thirknP~c-pc of intercalated pesticide, or small multiples less than about 10, preferably less than about 5 and more preferably less than about 3 of the layers, and still more preferably 1 or 2 layer6. In the preferred ~nhoflt--nt5 of this 30 invention, intercalation and delamination of every interlayer space is complete so that all or substan-tially all individual layers ~lAmin~te one from the other to form- separate platelet particles for admix-. ~
21 86~ q6 -- 56 -- PA~EN~r ApP
28682/128~1A
ture with the carrier or 601vent. In one embodiment,the compositions initially include all intercalated layered material, completely without exfoliation, to provide relatively low viscosities for transportation 5 and pumping until it is desired to increase viscosity via exfoliation. In cases where intercalation between some layers is incomplete, those layers do not delami-nate in the carrier or solvent, and form platelet particles comprising layers in a coplanar aggregate.
The effect of adding n~nl~sc~ particulate dispersed platelet particles, derived from the inter-calates, into an organic liquid carrier, typically is an increase in viscosity. Pesticide compositions comprising a solvent containing a desired loading of platelets obtained from exfoliation of the interca-lates and are outstandingly suitable as commercial products. Such compositions are viscous liquids or gels that resist leaking from packages and are easy to collect if spilled. The compositions according to the invention also are easily dissolved, dispersed or emulsified in an appropriate solvent by pesticide applicators, who then can apply the correct dosage of pesticide to the desired surface. Some viscous or gelled pesticide compositions can be packaged in water-soluble packaging. Such compositions resist leakage f rom the package if the package is damaged .
Accordingly, the pesticide applicator does not come in contact with the pesticide, and accidental spillage or leakage of the pesticide is essentially eliminated.
The following are specific clay:water-soluble polymer intercalate preparations to more particularly illustrate the activation of a layered material and are not to be construed as limitations . .~
2~86~9~
- 57 -- PAT~NT APPLICATIo~

thereon. These clay-polymer intercalates constitute one form of an activated clay, and can be used as a precursor to adding the intercalant pesticide.
Alternatively, water alone or an aqueous solution of 5 a water-miscible organic solvent is added to activate the clay prior to adding the intercalant pesticide.
In another embodiment, the clay i5 activated in the presence of an intercalant pesticide.
PxeParati4n of Clav-PVP ComPlexes Materials: Clay-sodium montmorillonite;
Intercalant polymer-PVP (mo-lecular weights of 10, 000 and 40, 000) .
To prepare clay (sodium montmorillonite)-PVP
15 complexes (i.e., intercalates), three different processes were used f or polymer intercalation to activate the clay:
1. Mixture of a 2% PVP/water solution with a 2% clay/water suspension in a ratio sufficient to provide a polymer concen-tration of at least about 8% by weight, preferably at least about 10% by weight, based on the dry weight of the clay .
2. Dry clay powder (about 8% by weight moisture) was gradually added to a 2%
PVP/water solution in a ratio suffi-cient to provide a polymer concentra-tion of at least about 8% by weight, preferably at least about 10% by 21 861 ~6 - 58 - PATENT A~?PLICATIOI~

weight, based on the dry weight OI the clay .
3. Dry PVP was mixed with dry clay, and the resulting mixture was hydrated with about 25 to about 50%, preferably about 35~ to about 40% by weight water, based on the dry weight of the clay, and then extruded .
Mixtures 1 and 2 were agitated at room temperature for 4 hours. The clay:PVP weight ratio was varied from 90:10 to 20:80.
The examples in Table 1 show that each method of preparation yielded a clay-PVP complex (intercalate), and that intercalation results do not depend upon a particular method of preparation ( l, 2, or 3 ) or upon the molecular weight of the intercalant polymer (PVP), but do depend upon the ratio of clay:PVP. In Table 1, data from x-ray diffraction patterns for clay-PVP complexes with different ratios of ~, vlle-l~s are summarized. The plot of this data is illustrated in Fig. 4. From this data (Table 1, Fig . 4 ) the stepwise character of intercalation while the polymer is being sorbed in the interlayer space between adjacent platelets of the montmorillonite clay is seen. There are increasing d(001) values from 12 (for clay with no sorbed PVP, i.e., Fig. 11) to a 24-25 A spacing between adjacent clay platelets with sorption of 20-30% PVP. Fig. 6 illustrates a d(001) value of 23.62 ~ for a PVP:clay weight ratio of 20:80.
The next step to 30-32 ~ spacing occurs when the sorbed PVP content is increased to 40-60%. Fig.
10 illustrates a d(001) value of 31.94 ~ ~or ~ 21~6196 28682/128~A
PVP:clay weight ratio o~ 50:50. Further increasing the sorbed PVP contcnt to 70-809~ increases the d(001) values to 40-42 A. Fig. 12 illustrates a d(001) value of 41 ~ for a PVP:clay weight ratio of 80:20. There are d(002) values together with d(001) values in x-ray diffraction patterns of all intercalates obtained (Table 1, Fig . 4 ) . This indicates the regularity of clay-PVP intercalate structures.
TABL~ ~
PVP, 561 d(001), A d(002), A
10 1 0.0 12.4 6.2 2 10.0 17.5 8.6 3 20.0 24.0 11.4 4 30.0 25.0 12.0 5 40.0 30.0 15.2 15 6 45.0 31.0 15.2 7 50.0 30.0 15.5 8 55.0 32.0 16.5 9 60.0 34.0 17.0 10 70.0 40.0 21.0 20 11 80. 0 42 . 0 21. 0 1 Percent by weight, based on the dry weight of the clay plus polymer.

- 6 0 - PATE NT APPr 28682/128~A
Prel~aratlon of ClaY-PVA Com~lexes Materials: Clay-sodium montmorillonite;
Intercalant polymer-PVA (de-gree of hydrolysis 75-99%, molecular weight 10,000).
To prepare clay (sodium montmorillonite)-PVA
complexes (i.e., intercalates), three different processe6 were used for polymer intercalation to activate the clay:
1. Mixture of a 296 PVA/water solution with a 2% clay/water suspension in a ratio sufficient to provide a polymer concen-tration of at least about 8% by weight, preferably at least about 10% by weight, based on the dry weight of the clay .
- 2. Dry clay powder was gradually added to a 2% PVA/water solution in a ratio sufficient to provide a polymer concen-tration of at least about 8% by weight, preferably at least about 10% by weight, based on the weight of the clay .
3. Dry clay was moisturized with PVA/water solution to a moisture content of 25%
to 8096, preferably about 35% to 40%
water, and then extruded.
The mixtures 1 and 2 were agitated at room _ temperature for 4 hours.
The weight ratio clay:PVA was varied from 80:20 to 20:80.

' ~' 2~86lq6 - 61 - PATI~NT APPLICATION

Some of the intercalates were studied by x-ray diffraction. These example6 6how that all method6 o~ preparation yielded the cospo6ite clay-PVA
complexe6 (intercalate6), and the re6ult6 of the intercalation do not depend upon a particular method of preparation (1, 2, or 3), the molecular weight of the intercalant polymer (PVA), or the degree of hydroly6is, but do depend on the clay:PVA ratio. In Table 2 data from x-ray diffraction patterns for clay-PVA complexes with different ratios of components are summarized. A plot of this data is illustrated in Fig. 5 . From this data ~Table 2 , Fig. 5), the step-wise character of increasing d(001) values from 12 (for clay with no sorbed PVA, i.e., Fig. 11) to 22-25 A spacing between adjacent platelets with sorption of 20-30% PVA is illustrated. Fig. 8 illustrates a d(001) value of 20.04 A for a PVA:clay weight ratio of 20:80. The next step to 30-33- A occurs when the sorbed PVA content increases to 35-50%. A further increase of the sorbed PVA content to 60-80% increases the d(001) values to 40-45 A.
Heating the clay-PVA intercalates at 120~C
for 4 hours did not significantly change the d(001) values (Table 2, Fig. 5). The change in d(001) value from 12.4 A to 9.6 A for the sample containing 0% PVA
illustrates that water is expelled from the clay, the spacing betYeen clay platelets is decreased.

-- 62 -- PATE~T APPT Tr~
28682/128~A
TAB~E 2 PVA%l d(001), ~ d(001), A
120~C
0.0 12.4 9.6 2 10 . 0 17 . o 16 . 8 3 20.0 23.0 22.0 5 4 30.0 25.0 24.0 5 35.0 32.0 32.0 6 40.0 31.0 30.0 7 45.0 33.0 32.0 8 50.0 32.0 32.0 10 9 60.0 42.0 42.0 1070 . 0 44 . 0 42 . 0 1180 . 0 45 . 0 44 . 0 1 Percent by weight, based on the dry weight of the clay plus PVA.
Specifically, Figs. 6 through 8 are x-ray diffraction patterns of blends of different water-soluble polymers with sodium bentonite clay. The patterns of Figs. 6 and 7 are taken from clay interca-lated with 2096 by weight polyvinylpyrrolidone (weight average molecular weight 10,000 for Fig. 6; 40,000 for Fig. 7) and 30% by weight sodium bentonite clay. The blends were formed by mixing the PVP and clay from a 2% solution of PVP and a 2% dispersion of sodium bentonite in a 1: 4 ratio, respectively. As shown, the PVP:clay complexed since no d(001) smectite peak appears at about 12 . 4 A ( i . e., see Fig . 11 for un-treated sodium bentonite clay). Similar results a~e ~ .l - 63 - l?AT~NT APPLICATION
28682/128~A
shown for 20% polyvinyl alcohol, 80% sodium bentonite, as shown in Fig. 8, blended in the same way and in the same ratio. An x-ray diffraction pattern for sodium bentonite containing no additives is presented Fig. 11 5 for comparison.
The d(OO1) peak of nonexfoliated (layered) and untreated sodium bentonite clay appears at about 12 . 4 A, as shown in the x-ray diffraction pattern for sodium bentonite clay (containing about 10% by weight 10 water) in Fig. 11 and in the lower x-ray diffraction patterns of Figs. 9 and 10. Fig. 9 includes x-ray diffraction patterns of sodium bentonite clay (mont-morillonite) and a PVP: clay complex that was obtained by extrusion of a blend of 20% by weight polyvinylpyr-rolidone (molecular weight 10,000) and 80% by weight sodium bentonite clay (containing a crystobalite impurity, having a d-spacing of about 4 . 05 A) with 35%
water based on the weight of dry clay plus polymer.
As shown in Fig. 9, the PVP and clay complexed since no d(OO1) smectite peak appears at about 12.4 A.
There are basal spacings with a d(OO1) peak of PVP:clay complex at about 24 A and d(O02) peak of PVP:clay complex at about 12 A, that shows close to regular structure of this intercalated composite with a PVP:clay ratio etaual to 1:4.
Fig. 10 contains x-ray diffraction patterns of sodium bentonite clay (montmorillonite) and PVP:clay complex that was obtained by extrusion of blend of 50% by weight polyvinylpyrrolidone (molecular weight 10,000) and 50% of sodium bentonite clay (containing a crystobalite impurity, having d-spacing of about 4.05 A) with 35% water based on the weight of dry clay plus polymer. As shown in Fig. 10, the ~ 2~û6196 - 64 - PATENT Appr~Tr~Tr~

PVP:clay complexed since no d(oOl) smectite peak appears at about 12 . 4 ~. There are basal spacings with a d(001) peak of the PVP:clay complex at about 32 A and a d ( 002 ) peak of PVP: clay complex at about 16 5 that shows close to regular structure of this interca-lated composite with a PVP:clay ratio equal to 1:1.
When mechanical blends of powdered sodium bentonite clay (containing about 10% by weight water) and powdered polyvinylpyrrolidone (PVP) polymer were mixed lO with water (about 75% by weight water), the polymer was intercalated between the bentonite clay platelets.
An exothermic reaction occurred that, it is theorized, resulted from the polymer being sufficiently bonded to the internal faces of the clay platelets for exfolia-15 tion of the intercalated clay.
Treatment of the sodium bentonite with anaqueous solution of the water-soluble polymer provides an activated clay that subsequently can be intercalat-ed with an intercalant pesticide, either containing or 20 lacking a polar moiety. It should be noted that exfoliation of an intercalated clay did not occur unless the bentonite clay included water in an amount of at least about 4% by weight, based on the dry weight of the clay. When inter-calating in a phyllo-25 6ilicate slurry, it has been found that at least about65% by weight water, based on total weight, provides easier mixing and faster migration of the polymer and pesticide into the spaces between platelets.
It also should be noted that exfoliation can 30 occur without shearing, i.e., the layered clay exfoli-ated naturally after sufficient intercalation of polymer or pesticide between the platelets of the layered bentonite, whether the intercalate was pre-~ .l -- 65 -- PATENT AppLIcATIr~N
Z8682/128~A
pared using sufficient water, e.g., at least about 20%by weight, preferably about 30% to about 100~6 by weight, or higher, based on the dry weight of the clay, for sufficient migration of the polymer or 5 pesticide into the interlayer spaces, and preferably also by extruding. ~xfoliation should be avoided until the intercalant pesticide has contacted the activated clay.
A number of compositions were prepared 10 containing intercalates (complexes~ formed by contact-ing sodium bentonite clay with an activating composi-tion comprising water and a water-soluble polymer.
Suf f icient sodium bentonite clay was added to the activating composition to provide a pre~erred weight 15 ratio of dry clay/polymer of 4:1 (80% by weight clay/20% by weight polymer) with sufficient water such that the resulting composition contained 35 to 40% by weight water for effective extrusion of the composi-tion through die openings of an extruder. The polymer 20 and water are mixed with the clay to complex (interca-late) the polymer between adjacent clay platelets.
The resulting polymer-intercalated clay then was contacted with an intercalant pesticide.
EXA~!PL3~
In general, a clay-polymer intercalate or an untreated clay are contacted with a pesticide, in the presence of water, to intercalate the pesticide between layers of the clay. Preferably, a water-miscible solvent is present in the water. An extru-sion step accelerates the process of intercalating the pesticide between the clay layers. A pesticide -- 6 6 -- PATENT APPLIQ~rION
28682/128~A
containing a polar moiety can be intercalated into either untreated clay, a clay activated with water, or a clay-polymer intercalate. A pesticide lacking a polar moiety is intercalated into a clay-polymer 5 intercalate. When an intercalant pesticide is added to the activated clay or the clay-polymer intercalant, the pesticide displaces the water and optional polymer from the space between adjacent clay platelets and is intercalated therein.
The following are nonlimiting examples of :
preparing a clay-pesticide intercalant from untreated clay .
Pre~aration of Clav-Herbicide Intercalates Materials: Clay-sodium montmorillonite;
Herbicide-2, 4-dichlorophen--- - oxyacetic - acid (2 , 4-D), bu-tyl ester To prepare clay (sodium montmorill-onite)-2,4-D ester complexes (i.e., intercalates), three different processes are used for intercalation:
l. Mixture of a 2% 2,4-D butyl ester/water dispersion or emulsion with a 296 clay/water suspension in a ratio suffi-cient to provide a 2, 4-D butyl ester concentration of at least about 896 based on the dry weight of the clay.
2. Dry clay powder (about 8% by weight moisture) is gradually added to the 2%
2, 4-D butyl ester/water dispersion or emulsion in a ratio sufficient to pro-vide a 2, 4-D butyl ester ~_u--c~..L~ ~tion ~ j ~
21 ~61 '~6 - 6~ - PATENT APPLICATTOX
28682/128~.A
of at least about 8% based on the dry weight of the clay.
3 . 2, 4-D butyl ester (technical grade) is mixed with dry clay, the mixture is hy-drated with 35 to 38% of water, based on the dry weight of the clay, and then extruded .
Mixture6 1 and 2 are agitated at room temperature f or 4 hours .
The intercalation and exfoliation methods of the present invention yield clay-2, 4-D butyl e6ter intercalates, and the results of the intercalation do not depend upon a particular method of preparation ( 1, 2 , or 3 ), but do depend on the quantity of organic pesticide compound sorbed between clay platelets.
EXANPLE
PreParation of Clav-Insecticide Intercalates Materials: Clay-sodium montmorillonite;
Insecticide-chlorpyrif 05 To prepare clay (sodium montmorillonite)-chlorpyriphos complexes (i.e., intercalates), three different processes are used for pesticide intercala-tion:
1. Mixture of a 2% chlorpyrifos/water dis-persion with a 2% sodium montmorill-onite clay/water suspension in a ratio sufficient to provide a chlorpyrifos concentration of at least about 8 %
based on the dry weight of the clay.

~ ~~ 2~86~96 2. Dry clay powder is gradually added to a 2% chloripyrifos/water dispersion in a ratio suf f icient to provide a chlor-pyrifos .~ c~ tion of at least about 8% based on the dry weight of the sodi-um montmorillonite clay.
3. Dry sodium montmorillonite clay is moisturized with chlorpyrifos/water dispersion to 20-80% by weight water, and then eYtruded.
The mixtures 1 and 2 are agitated at room temperature for 4 hours. The intercalation method yields a clay-chlorpyrifos intercalate regardless of the method of preparation.
In another example, a dispersion or emulsion of 30% by weight 2,4-dichlorophenoxy acetic acid (2, 4-D) and 70% by weight dicamba is prepared in water, at a concentration of 45% by weight of the 2, 4-D and dicamba mixture. Thirty grams of the 2, 4-D/dicamba mixture is added to a 50 ml (milliliter) beaker, and while this mixture is mixed vigorously, 1.5 grams of sodium montmorillonite (i.e., POLARGEL NF
from A~COL International Corporation) is added. The weight ratio of clay to ( 2, 4-D dicamba mixture) is -1. 9 . The mixture is vigorously mixed and heated for hour at 8 5 ~ C .
The heated mixture is allowed to cool to room temperature and the resulting product is subject-ed to x-ray diffraction. The x-ray diffraction pattern shows that the 2, 4-D/dicamba is intercalated in the clay because the periodicity, or d(001) value, of the clay is increased from 12 . 4 ~, showing that ~ .~
~186196 2,4-D and dicamba are intercalated between adjacent clay platelets.
All methods of the present invention used for intercalation yield clay-pesticide intercalates, 5 and the results of the intercalation do not depend upon method of preparation ( 1 , 2 , or 3 ), but do depend on the quantity of pesticide sorbed between clay platelets .
The following are further illustrative and 10 nonlimiting examples of the present invention. The following examples illustrate intercalated layer materials wherein the intercalant pesticide is ~
trif luoro-2 - 6-d initro-N, N-dipropy 1 -p-toludine, having the common name trif luralin and available from Dow 1~ Elanco, I dia~apolis, IN.

~ .~
21g6'19~
~ 7 0 - PATENT APPr.
28682/128~A
EXAi~PLE #1 #2 #3 #4 #5 #6 Belle Yellow Clayl 2004 200 500 400 PDTQ2 Orgamo Clay 200 200 IVP (Surface Modified Clay)3 5 Deioni2cd Water 90 150- 150-(pH 3) 170 170 Deior~ized Water 60 (normal pH) Trifluralm 60 142 86 101 214 171 Solvent 359 509 701~ 909 439 15 i an ummodified tiodium bdntonlt~ clay powdcr having particles collected on a 325 mesh sieve (U.S. Sieve or Tyler), i.e., zt least 44 microns m diameter;
2 a sodium bentonite clay surface treated with a qttaternary ammortium compoumd;
3 a sodium bentonite clay surface trettted with 20 % by WeiBht t~ 'rJ '' ' 4 amoumts of all irlgre iients are expressed as grams;
polyeihylene glycol, PLURACOL E4000, available from BASF Corporation, Parsippamy, NJ;
6 polyethyleneglycol,PLURACOLE-400,availablefromBASFCorporation,Parsippamy, NJ;
7 i~ulJ ,,!t,,'' ' , PVP K-15, available from GAF Chemicais Corp., Wayne, NJ;
25 8 polyvmyl alcohol, VINOL 540, available from Air Products amd Chemic~ils, inc., Ailentown, PA;
9 isopropyl alcohol;
10 xylene; amd Il ethylene glycol monohutyl ether.

.

- 71 - PATE~T APPL~CATION
Z8682/128~A
EXAMPLE #7a #7b #8a #8b #9it ~9b Bdle Ydlow Clayl 400 200 200 2004 PDTQ2 Olgamo Clay IVP (Surface Modified Clay)3 200 200 5Deionized Water (pH 3) Deionized Water 70 170- 130 130 96 (normal pH) 180 Tnfluralin 300 150 153 120 86 102 Solvent 389 249 229 2611 15 1 am unmodified sodium bentoni~e clay powder havm~ particles collected on a 325 mesh sieve (U.S. Sieve or Tyler)~ i.c., at l~asl 44 microns in diameler;
2 a sodium bentonite clay surface treated with a quatern-ry ammonium compound;
3 a todium bentonite clay surface treated with 205~ by wei~ht pulJ ~,..,~., ' ' 4 amoumts of all ingredients are exprcssed as grams;
polyethylene glycol, PLURACOL E-4000, available from BASF Corponation, Parsippamy, N3;
6 polyethylene glycol, PLURACOL E-400, available from BASF Corporation, Parsippany, N~;
7 t,u'~ 'p"l ' ' PVP K-15, available from GAF Chemicals Corp., Wayne, N3;
8 polyvmyl alcohol, VINOL 540, available frnm Air Products amd Chemicals, hnc., Allentown, PA;
9 isopropyl ~Icohol;
10 ~ylene; amd Il ethylene glycol monobutyl ether.

~ .~

- 72 - PATENT APPT.Tr~ r~
28682/12842~
EXAMPLE #lOa #lOb #10c #lQd #lla #llb #llc Belle Yellow Clayl 300 300 200 200 200 200 200 PDTQ2 Organo Clay IVP ~Surface Modi-5 fied Clay)3 Deionized Water4 110 (pH 3) Deionized Water4 190-210 130-140 88 80 100 95 (normal pH) 10 Trifluralm4 128 154 102 94 150 70 60 15 Solvent 3111 3911 2611 2411 209 109 109 an ummodified sodium bentonite clay powder havmg particles collected on a 325 mesh sieve (U.S. Sieve or Tyler), i.e., at least 44 microns in diameter;
a sodium bentonite clay surface treated with a quaternary ammonium compoumd;
3 a sodium bentonite clay surface treated with 2096 by weight t,~
2 0 4 amoumts of all ingredients are e~pressed as grams;
5 polyethylene glycol, PLURACOL E-4000, available from BASF Corporation, Parsipp;my, NJ;
6 polyethylene glycol, PLURACOL E-400, available from BASF Corporation, Parsippany, NJ;
2 5 7 ~1) ....jl~, ' ' , PVP K-15, available from GAF Chemicals Corp., Wayne, NJ;
8 polyvinyl alcohol, VINOL 540, available from Air Products )md Chemicals, Inc., Allentown, PA;
9 isopropyl alcohol;
10 ~ylene; amd 3 0 11 etbylene glycol monobutyl etber.

21 861 ~

28682/128~A
X-ray diffraction patterns for wet and/or dry intercalated pesticides of Examples #1 through #llc were taken, and are presented herein as Figs. 13-22. In Figs. 13-30, the peak at 11.21 A is attributed 5 to trifluralin that is in excess or crystallized on the surfacQ of the clay. The intercalated pesticides of Examples #1-#llc were prepared from activated clay in accordance with the methods described in the previous examples. In each example, crystallization 10 of trifluralin on the clay was minimized because crystallized trifluralin is not available for interca-lation .
Example 1 and Figs. 13 and 14 show that 2396 trifluralin was intercalated into the clay. Attempts 15 to intercalate trifluralin into a quaternary ammonium-treated clay failed in Examples 2 and 3.
In particular, Fig. 13 shows that the intercalated cIay has a periodicity of 18 . 8 A, an increase from a periodicity of 12 . 4 A for untreated 20 clay. ~he wet sample was dried in a vacuum oven (10-3 torr) at 60~C for 48-60 hours causing the trifluralin to sublimate from the clay, as illustrated in Fig. 14, i.e., periodicity of 12.37 A. Importantly, Fig. 14 illustrates that a pesticide can be released from the 25 intercalate to perform its intended function.
In preparing the intercalates of Examples #1-#llc, it was found that warming the activated clay/trifluralin mixture to about 40~C to about 60~C, without vacuum, and extruding the warm mixture produc-30 es a more homogeneous intercalated product. However,because trifluralin sublimates, heating the mixture above about 60~C to 65~C produces a product having high amounts of crystalline trifluralin. It is ~ 2186Iqf - 74 - PATEN~ APPLICATION

envisioned that other pesticides, that do not subli-mate, can be heated up to ~bout 80~C without adverse ef f ects .
Examples #2 and #8a were prepared using about 40% trifluralin. Each intercalated product showed significant crystallization of trifluralin.
Arc-7rtlin~ly, the upper limit for intercalating tri-fluralin is about 40%, and preferably about 30%.
Examples #ga, #9b, #lOd, and #llc had very little visible trifluralin crystals, ~howing that 3096 by weight trifluralin can be intercalated into an acti-vated clay. Example #9a utilized a clay that was surface treated with polyvinylpyrrolidone, whereas the clay used in Examples #9b, #lod, and #llc had 20% PVA, 10% PVA, and 10% PEG, respectively, intercalated into the clay prior to contact with the trifluralin.
Examples #gb and #lOd were extruded twice. X-ray di~fraction patterns for Examples #9a, #gb, #lod~ and #llc are set forth in Figs. 15-22.
With respect to Figs. 15 and 16 and Example #9a, the surface-treated clay, prior to intercalation has a periodicity of about 23 A. Fig. 15 shows that periodicity increased to 34.9 A after intercalation of trif luralin into the clay . Fig. 16 is an x-ray diffraction after drying the intercalated clay showing that trifluralin is released from the intercalated clay .
Figs. 17 and 18 are x-ray diffraction patterns of Example #9b showing trifluralin is inter-calated (i.e., periodicity of 17.38 A), and after drying overnight at 67~C without a vacuum remains intercalated ( i . e ., Fig . 18, periodicity 17 . 54 ~) .
Figs 19-22 show similar results, including release of ~ 2186196 28682/128~A
the pesticide, for Examples ~lOd and #llc using less PVA or using PEG as the intercalant polymer.
E2LaNPLE 12~L
200g Belle Yellow clay (powder) 20g PVA (powder mixed dry in clay) 94g Trifluralin 115g Deionized water (normal pH) No organic solvents were used in Example 12a. The ingredients were admixed and heated at about 10 40~C to about 60~C during mixing, and the resulting mixture was extruded twice. The extruded intercalated product was dried at 29~C. Trifluralin crystallized on the sides of the mixing vessel. Small crystals of trifluralin were visible in the final product. The 15 x-ray diffraction patterns of wet and dry samples of Example 12a are set forth in Figs. 23 and 24. Figs.-23 and 24 show that trifluralin intercalated between platelets of the clay ( i . e., Fig . 23, periodicity is 19 . 03 AA) and is released f rom the intercalate ( i . e ., Fig. 24, periodicity is 12 . 63 A) .
EXANPLE 12b 200g AEG clay (granular) 20g PVA (powder mixed dry in clay) 94g Trifluralin 115g Deionized water (normal p~) Granular clay was used in Example 12b. The AEG clay is a granular sodium bentonite having a majority of the particles (i.e., at least 60% by weight) ranging from 210 to 840 microns in diameter.

~. 2~86196 In particular, a maximum of 20% by weight of the particles are larger than 840 microns in diameter, and a maximum of 20% by weight of the particles are smaller than 210 microns in diameter. The granular 5 clay absorbed water to activate the outer portion of the granular, but insufficient water was present to completely hydrate the granules. Therefore, the granules did not absorb the water evenly, causing the granules to clump. Clumping of the granules caused 10 the trif luralin to coat the outside of the clumps and form crystals . Trif luralin crystals were observed in the finished intercalated pesticide even after two extrusions. The trifluralin, therefore, was not evenly dispersed throughout the clay. The product was 15 dried at 33~C. The x-ray diffraction patterns of wet and dry samples of Example 12b are set forth in Figs.
25 and 26.
The x-ray diffraction patterns show that a minor portion of the trifluralin was intercalated, 20 i.e., the relatively small peak at 19.51 ~ and the large trifluralin peak at 11.21 A in Fig. 25. A
majority of the trifluralin, therefore, merely surface coated the clay granules. Fig. 26 further illustrates that the majority of the trifluralin surface coated 25 the granules because the trifluralin sublimed during drying to yield essentially nonintercalated clay, i.e., periodicity of 12.46. Using an increased amount of water when using a granular clay would overcome this difficulty 2 ~ 861 96 EXAIIPLE 12c 200g Belle Yellow clay (powder) 20g PVA (powder mixed dry in clay) 94g Trifluralin 23 . 5q isopropyl alcohol 115g Deionized water (normal pH) Example 12c used a combination of isopropyl alcohol and PVA to activate the clay. Example #lOD
was 6imilar to Example 12c, except in Example #loD
only 88g of water was used and a glycol ether was used instead of isopropyl alcohol. The intercalated product6 of Examples #loD and 12C di~fer in appearance only by color, wherein the pesticide of Example 12c is a darker orange color. ~he intercalated pesticide of Example 12c was dried at 38~C. X-ray di~fraction patterns of wet and dry samples of the intercalated pesticide of Example 12c are set forth in Figs. 27 and 28, which illustrate intercalation and release of trif luralin .
Examples 13a-13d illustrate the effect of adding 10%, 20%, 30%, and 40% trifluralin, by weight, to clay.
EX~SPLE 13a 200g Belle Yellow clay 22.2g Trifluralin (10%) 88 . 8g Deionized water (normal pH) (40% by weight of clay and trif luralin) ~ 2186196 28682/128~A
~Y~ PLE 13b 200g Belle Yellow clay 50g Trifluralin (20%) 87.5g D~ n;7pd water (normal pH) (359~ by 5 weight of clay and trifluralin) E~PLE 13c: =
200g Belle Yellow clay 86g Trifluralin (30%) 100g Deionized water (normal pH) (35% by 10 weight of clay and trifluralin) EJ~fPLE8 13d 200g ~3elle Yellow clay 133.3g Trifluralin (40%) 100g Deionized water (normal pH) (30% by 15 weight of clay and trifluralin).
Examples 13a-13c each were extruded once. Example 13d was extruded twice. The trifluralin was easily melted in the absence of solvents, but tended to crystallize quickly. Example 13a was too wet for easy processing.
20 X-ray diffraction patterns of wet and dry samples of Examples 13a-13d are set forth in Figs. 29 and 30.
Figs. 29 and 30 show that trifluralin is intercalated and is released. The large peak at 11.26 A for Example 13d (i.e., 4096 trifluralin) in Pig. 29 25 shows ~hat excess trifluralin is present, and no further trifluralin can be intercalated into the clay.

21, 86~ ~6 As previously stated, the intercalate containing the intercalant pesticide, after drying, can be pelletized to provide a useful pesticide product. Alternatively, the pellotized intercalate 5 can be used as a composition ingredient, and admixed with other solid ingredients to provide a solid pèsticide composition. Finally, the intercalate, either as is or after exfoliation, can be dispersed in an organic liquid, to provide a viscous or a gelled 10 pesticide composition. The viscosity of the composi-tion formed by adding the intercalate or exfoliate thereof is ~9PrPn~ont upon intercalate loading, as well as a temperature, pH, and water content of the compo-sition .
It is preferred that platelet loading in a liquid carrier is less than a~out 10%. Platelet particle 1 OAt9; nqC within the range of about 0 . 01% to - about 40% by weight, preferably about 0.05% to about 20%, more preferably about 0.5% to about 10%, signifi-20 cantly PnhAnsP~ viscosity of a pesticide compositioncontaining a liquid carrier and a layered material having an intercalant pesticide incorporated therein.
In general, the amount of platelet particles incorpo-rated into a liquid carrier, such as a polar solvent, 25 e.g., a glycol or polyol, such as glycerol, is less than about 20% by weight of the mixture, and prefera-bly from about 0. 01% to about 20% by weight of the pesticide composition mixture, more preferably from about 0 . 01% to about 10% by weight of the mixture, and 30 most preferably from about 0. 01% to about 5% by weight .
When an organic liquid, or solvent, is added to the intercalate or exf oliate thereof, the mixture 21 861 q6 - 80 - PATE~r AppT Tr 28682~1284A
is mixed until homogenous, and often heated, to form a more viscous gel before cooling to room temperature (i.e., 24~C) to measure the viscosity (i.e., on a Brookfield viscometer, spindle #4, unless otherwise 5 noted). Mixing a composition at room temperature typically results in a viscosity of about 2, 000 to about 3, 000 centipoises (cps), wherein heating the composition resulted in viscosities of about 3, 500 to about 4,000 centipoises (80~C) and about 7,000 to about 8,000 centipoises (100~C), all viscosities being measured at 24~C. Heating to 145~C, then cooling to room temperature, increased the viscosity to about 200,000 to about 600,000 centipoises.
Various organic liquids can be used to 15 provide a viscous, gelled, or thixotropic composition.
Preferably, an organic liquid is added to an interca-late made using an intercalant polymer and/or that is exfoliated. Nonlimiting examples of organic solvents that can be used include methanol, i60propyl alcohol, 20 propylene glycol, glycerol, l-propanol, acetone, ethanol, ethylene glycol, and 1, 4-butanediol. An emulsified combination of silicone oil and water also provided a gel. The organic liquid can be used alone, in combination with water, or in combination with 25 other organic liquids.
By increasing the pH substantially outside the range of about 6 to about 10, the viscosity of the composition is increased to provide a thixotropic gel of viscosity 1,500,0~0 centipoises, at 24~C, without 30 heating. The pH is adjusted by shearing all compo-nents, except an acid or base, in a blender for 3 minutes, then adding the acid or base, and shearing for an additiona; minute.

PATENT APPLICATION
2868Z/lZ84A
Numerous modif ications and alternative omh~-l;r~nts of the invention will be apparent to those skilled in the art in view of the f oregoing descrip-tion. Accordingly, this description is to be con-5 strued as illustrative only and is for the purpose ofteaching those skilled in the art the best mode of carrying out the invention. The details of the process may be varied substantially without departing from the spirit of the invention, and the exclusive 10 use of all modif ications which come within the scope of the appended claims iB reserved.

Claims (63)

1. An intercalate, capable of being exfoliated, comprising a layered material and an intercalant pesticide, formed by contacting the layered material, having adjacent platelets of said layered material, with water or an aqueous solution of a water-soluble intercalant polymer to form an activated layered material, and contacting the activated layered material with an intercalant pesticide to form the intercalate by sorption and complexing of the intercalant pesticide between adjacent spaced layers of the activated layered material to expand the spacing between a predominance of the adjacent platelets of the activated layered material to at least about 5 .ANG., when measured after sorption of the intercalant pesticide and drying to a maximum of 5% by weight water.

2. The intercalate of claim 1 wherein the concentration of intercalant pesticide contacting the activated layer material is at least about 2% by weight, based on the weight of water, water-soluble polymer, and intercalant pesticide.

3. The intercalate of claim 2 wherein the concentration of intercalant pesticide is at least about 5% by weight.

4. The intercalate of claim 3 wherein the concentration of intercalant pesticide is at least about 30 % by weight.

5. The intercalate of claim 1 wherein the layered material is activated by water.

6. The intercalate of claim 5 wherein a water-miscible organic solvent is present in the water.

7. The intercalate of claim 1 wherein the layered material is activated by an aqueous solution of a water-soluble intercalant polymer.

8. The intercalate of claim 1 wherein the concentration of intercalant pesticide is about 0.01%
to about 40% by weight, based on the dry weight of the layered material.

9. The intercalate of claim 8 wherein the concentration of intercalant pesticide is about 0.1%
to about 35% by weight, based on the dry weight of the layered material.

10. The intercalate of claim 9 wherein the concentration of intercalant pesticide is about 5% to about 30% by weight, based on the dry weight of the layered material.

11. The intercalate of claim 1 wherein the concentration of intercalant pesticide is at least about 8% by weight, based on the dry weight of the layered material.

12. The intercalate of claim 1 wherein the concentration of the intercalant polymer is at least about 16% by weight, based on the dry weight of the layered material, to achieve spacing between adjacent platelets of said activated layered material of at least about 10 .ANG..

13. The intercalate of claim 1 wherein the concentration of the intercalant polymer is at least about 35% by weight, based on the dry weight of the layered material, to achieve spacing between adjacent platelets of said activated layered material of at least about 20 .ANG..

14. The intercalate of claim 1 wherein the concentration of the intercalant polymer is at least about 55% by weight, based on the dry weight of the layered material, to achieve spacing between adjacent platelets of said activated layered material of at least about 30 .ANG..

15. The intercalate of claim 1 wherein the intercalant pesticide contains at least one polar moiety.

16. The intercalate of claim 6 wherein the intercalant pesticide lacks a polar moiety.

17. The intercalate of claim 15 wherein the polar moiety is selected from the group consisting of a carboxylic acid, a salt of a carboxylic acid, an ester, an amide, an anhydride, a ketone, an aldehyde, cyano, nitro, thiocarbamate, amino, carbamic, phosphate, thio-phosphate, sulfoxide, carboximide, urea, sulfone, phos-phorothioate, phosphorodithioate, thiourea, dithiocarbamate, phosphoramidodithioate, methylsulfonyl, phosphonate, sulfamide, phosphoramide, sulfonate, dithiocarbonate, hydroxyl, sulfate, sulfinate, sulfamate, or phosphinate.

18. The intercalate of claim 15 wherein the polar moiety has two adjacent atoms that are covalently bonded, and the two atoms have a difference in electronegativity of at least about 0.5 electronegativity units.

19. The intercalate of claim 1 wherein the pesticide is selected from the group consisting of fungicides, insecticides, herbicides, acaricides, nematocides, rodenticides, miticides, repellents, growth regulators, larvacides, and mixtures thereof.

20. The intercalate of claim 1 wherein the pesticide comprises an herbicide.

21. The intercalate of claim 20 wherein the herbicide is selected from the group consisting of tri-fluralin, 2,4-D, dicamba, and mixtures thereof.

22. The intercalate of claim 1 wherein the pesticide comprises an insecticide.

23. The intercalate of claim 22 wherein the insecticide is chlorpyrifos.

24. The intercalate of claim 1 wherein the weight ratio of intercalant polymer to layered material is at least 1:20.

25. The intercalate of claim 1 wherein the weight ratio of intercalant polymer to layered material is at least 1:4.

26. The intercalate of claim 1 wherein the weight ratio of intercalant pesticide to layered material is at least about 1:2.

27. The intercalate of claim 1 wherein the concentration of intercalant polymer is at least about 0.1% by weight, based on the weight of water and polymer.

28. The intercalate of claim 27 wherein the concentration of intercalant polymer is at least about 2% by weight.

29. The intercalate of claim 1 wherein the concentration of intercalant polymer is at least about 2% by weight, based on the dry weight of layered material, wherein said intercalant polymer has a functionality selected from the group consisting of an aromatic ring, a carboxyl, a hydroxyl, a carbonyl, an ether, an ester, an amine, an amide, an SOx, a POx, wherein x=2, 3, or 4, and mixtures thereof.

30. The intercalate of claim 1 wherein the intercalant polymer is selected from the group consisting of polyvinylpyrrolidone, poly(vinyl alcohol), polyvinylimine, polyacrylic acid, poly(methacrylic acid), poly- (methacrylamide), poly (N, N-dimethylacrylamide), poly (N-acetamideacrylamide), poly (N-aceto-methamido-acrylamide), polyvinyloxazolidone, polyvinylmethyloxazolidone, poly-oxyethylene-polyoxy-propylene block copolymers, polyethylenimine, and copolymers and mixtures thereof.

31. The intercalate of claim 30 wherein the intercalant polymer is polyvinyl alcohol.

32. The intercalate of claim 30 wherein the intercalant polymer is polyvinylpyrrolidone.

33. The intercalate of claim 30 wherein the intercalant polymer has a weight average molecular weight in the range of about 100 to about 100,000.

34. A method of intercalating a phyllosilicate with a pesticide comprising:
contacting the phyllosilicate, having adjacent phyllosilicate platelets, with an activator comprising water and, optionally, a water-soluble polymer, a water-miscible organic solvent, or a mixture thereof, to form an activated phyllosilicate, and contacting the activated phyllosilicate with an intercalant pesticide to achieve intercalation of said intercalant pesticide between said adjacent phyllosilicate platelets in an amount sufficient to space said adjacent phyllosilicate platelets a distance of at least about 5 .ANG..

35. The method of claim 34, further including the step of separating the platelets of the pesticide-intercalated phyllosilicate into predominantly individual platelets.

36. A pesticide composition comprising an organic liquid carrier in an amount of about 40% to about 99.95% by weight of the composition, and about 0.05% to about 60% by weight of an intercalated phyllosilicate material, said intercalated phyllosilicate material formed by contacting a phyllosilicate, having adjacent phyllosilicate platelets, with water and, optionally, an intercalant polymer, a water-miscible organic solvent, or a mixture thereof, to form an activated phyllosilicate, and contacting the activated phyllosilicate with an intercalant pesticide to achieve sorption of the intercalant pesticide between adjacent spaced layers of the phyllosilicate sufficient to expand the spacing between a predominance of the adjacent phyllosilicate platelets to at least about 5 .ANG., when measured after sorption of the intercalant pesticide and at a maximum water content of about 5% by weight, based on the dry weight of the phyllosilicate.

37. The composition of claim 36 wherein the intercalated phyllosilicate is exfoliated into a predominance of single platelets having said intercalant pesticide complexed onto said platelet surfaces.

38. A composition of claim 36 wherein the organic liquid carrier is selected from the group consisting of alcohols, ketones, aldehydes, esters, glycols, glycerols, ethers, and mixtures thereof.

39. The composition of claim 36 wherein the organic liquid carrier is a monohydric alcohol having 1 to about 5 carbon atoms.

40. The composition of claim 36 wherein the organic liquid carrier is a polyhydric alcohol selected from the group consisting of glycols, glycerols, and mixtures thereof.

41. The composition of claim 36 wherein the intercalated phyllosilicate material is free of a compound having an onium ion or a silane coupling agent.

42. The composition of claim 36 having a viscosity of at least 5000 centipoise.

43. The composition of claim 36 wherein the composition is a thixotropic gel.

44. A pesticide composition comprising the intercalate of claim 1, in a concentration of about 0.05% to about 99.5% by weight, and an inert carrier.

45. The pesticide composition of claim 44 wherein the inert carrier is a solid selected from the group consisting of calcined clay, ground corn cobs, sawdust, silica, wood chips, sand, and mixtures thereof.

46. A method of manufacturing a pesticide composition comprising an organic liquid and a phyllosilicate intercalate comprising:

( a ) contacting a phyllosilicate with an activator comprising water and, optionally, a water-soluble polymer, a water-miscible organic solvent, or a mixture thereof, to form an activated phyllosilicate;
and contacting the activated phyllosilicate with an intercalant pesticide, wherein the concentration of said intercalant pesticide is at least about 0.01%
intercalant pesticide, based on the dry weight of the phyllosilicate, to form an intercalate having said intercalant pesticide intercalated between said adjacent phyllosilicate platelets in an amount sufficient to space said adjacent phyllosilicate platelets to a distance of at least about 5 .ANG.; and (b) combining the intercalate with said organic liquid.

47. The method of claim 46 wherein the intercalate is exfoliated after step (a).

48. The method of claim 47 wherein at least 80% of the intercalate is exfoliated.

49. A pesticide composition comprising an intercalate, together with an organic solvent, said intercalate formed by contacting a layered material, having a moisture content of at least about 4% by weight, with an intercalant polymer to form an activated layered material by sorption and complexing of the polymer between adjacent spaced layers of the layered material to expand the spacing between a predominance of the adjacent platelets of said layered material to at least about 5 .ANG., when measured after sorption of the intercalant polymer and drying to a maximum of 5% by weight water; and by contacting the activated layer material with an intercalant pesticide to provide the intercalate, wherein the intercalant pesticide is sorbed and complexed between adjacent spaced layers of the layered material.

50. The composition of claim 49 wherein said layered material has a moisture content of about 4% to about 5000% by weight, capable of dissolving said intercalant polymer, based on the dry weight of said phyllosilicate.

51. The composition of claim 49 wherein the moisture content is about 30% to about 40% by weight.

52. The composition of claim 49 wherein the moisture content is about 35% to about 40% by weight.

53. The composition of claim 49 wherein the moisture content is about 5% to about 50% by weight water, based on the dry weight of said phyllosilicate.

54. The composition of claim 53 wherein the moisture content is about 7% to about 100% by weight, based on the dry weight of the phyllosilicate.

55. A method of manufacturing a pesticide composition containing about 10% to about 99.95% by weight of an organic liquid and about 0.05% to about 60% by weight of an intercalated layered material, said intercalated layered material having a pesticide intercalated between and bonded to adjacent platelet surfaces thereof through a bonding mechanism selected from the group consisting of ionic complexing, electrostatic complexing, chelation, hydrogen bonding, dipole/dipole, Van Der Walls forces, and any combination thereof, comprising:
(a) contacting a layered material with water and, optionally, a water-soluble intercalant polymer, a water-miscible organic solvent, or a mixture thereof, to form an activated intercalate having said polymer intercalated between said adjacent platelets in an amount sufficient to space said adjacent platelets a distance of at least about 5 .ANG.;
(b) contacting the activated intercalate with an intercalant pesticide to form an intercalate having said pesticide intercalated between adjacent platelets of the layered material;
(c) combining the intercalate from (b) with the organic liquid; and (d) exfoliating the spaced platelets of said intercalate into predominantly individual platelets.

56. The method of claim 55 wherein (a) and (b) are performed stepwise.

57. The method of claim 56 wherein (a) is performed prior to (b).

58. The method of claim 55 wherein (a) and (b) are performed simultaneously.

59. The method of claim 55 wherein said layered material is a phyllosilicate and the phyllosilicate is contacted with about 4% to about 5000% by weight water, based on the dry weight of said phyllosilicate.

60. The method of claim 59 wherein the phyllosilicate is contacted with about 30% to about 50% water, based on the dry weight of the phyllosilicate.

61. A method of manufacturing a pesticide composition comprising an organic liquid and a phyllosilicate intercalate comprising:
admixing the phyllosilicate with a water-soluble intercalant polymer and water to form an intercalating composition, wherein the weight ratio of the intercalant polymer to phyllosilicate is at least 1 to about 20, and the concentration of said water-soluble intercalant polymer is at least about 5% up to about 900%, based on the dry weight of the phyllosilicate, to form an activated intercalate having said intercalant polymer intercalated between said adjacent phyllosilicate platelets in an amount sufficient to space said adjacent phyllosilicate platelets to a distance of at least about 5 .ANG.;
admixing the activated intercalate with an intercalant pesticide to form an intercalate having said intercalant pesticide intercalated between adjacent phyllosilicate platelets; and combining the intercalate with said organic liquid.

62. The method of claim 61 further comprising the step of exfoliating the intercalate into a predominance of single platelets having said inter-calant pesticide complexed onto said platelet surfaces.

63. The method of claim 62 wherein at least 90% by weight of the intercalate is exfoliated into single platelets.