CA1170856A - Emulsifiable concentrate formulations compatible with water and liquid fertilizer - Google Patents
Emulsifiable concentrate formulations compatible with water and liquid fertilizerInfo
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- CA1170856A CA1170856A CA000348806A CA348806A CA1170856A CA 1170856 A CA1170856 A CA 1170856A CA 000348806 A CA000348806 A CA 000348806A CA 348806 A CA348806 A CA 348806A CA 1170856 A CA1170856 A CA 1170856A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- Pest Control & Pesticides (AREA)
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- Agronomy & Crop Science (AREA)
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- Wood Science & Technology (AREA)
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Abstract
ABSTRACT OF THE DISCLOSURE
This invention provides an emulsifier composition comprising, in combination: (1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8-20 aliphatic alcohols, and (2) one or more amines selected from the group consisting of:
(a) fatty tertiary amines of the formula R1N(R)2; (b) fatty amine oxides of the formula R1?(CH2CH2OH)2 ;
(c) beta-amines of the formula H3CCH(NH2)R1; (d) amide-bridged tertiary amines of the formula R1CON(CH2)3N(R)2;
(e) ethoxylated tertiary amines of the formulae:
(i) R1N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1(CH2)3N(CH2CH2OH)2;
and (f) polypropoxylated low molecular weight tertiary amines;
where R is a C1-5 alkyl radical and R1 is a C8-18 aliphatic hydrocarbon radical; and wherein the weight ratio of com-ponents (I) to (2) is within the range of about 1:1 to about 10:1. Emulsifier concentrate formulations are also disclosed comprising the above emulsifier composition and at least one biologically-active compound selected from the group consist-ing of acetanilides, thiocarbamates and anilines. The invention provides stable emulsifiable concentrate formulations which are physically compatible with both water and liquid fertilizers.
This invention provides an emulsifier composition comprising, in combination: (1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8-20 aliphatic alcohols, and (2) one or more amines selected from the group consisting of:
(a) fatty tertiary amines of the formula R1N(R)2; (b) fatty amine oxides of the formula R1?(CH2CH2OH)2 ;
(c) beta-amines of the formula H3CCH(NH2)R1; (d) amide-bridged tertiary amines of the formula R1CON(CH2)3N(R)2;
(e) ethoxylated tertiary amines of the formulae:
(i) R1N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1(CH2)3N(CH2CH2OH)2;
and (f) polypropoxylated low molecular weight tertiary amines;
where R is a C1-5 alkyl radical and R1 is a C8-18 aliphatic hydrocarbon radical; and wherein the weight ratio of com-ponents (I) to (2) is within the range of about 1:1 to about 10:1. Emulsifier concentrate formulations are also disclosed comprising the above emulsifier composition and at least one biologically-active compound selected from the group consist-ing of acetanilides, thiocarbamates and anilines. The invention provides stable emulsifiable concentrate formulations which are physically compatible with both water and liquid fertilizers.
Description
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The invention herein pertains to the field of emulsifier compositions and emulsifiable concentrate formulations having biological activity, e.g., as herbicides, and having as the active ingredient thereof at least one compound selected from the group consisting of substituted acetanilides, thio-carbamates and anilines.
The prior art relative to emulsifiable concentrate (EC) formulations includes a wide variety of active ingredients and emulsifier/surfactant systems therefor. Such EC's are suitable for a variety of biological and agricultural utilities, both plant and animal, e.g., on soil or plants as herbicides, her-bicidal antidotes, plant growth regulators, nematocides, bac-tericides, fungicides, insecticides, soil fumigants, etc.
In practice, the EC containing the biologically-active ingredient is diluted in water and/or liquid fertilizer before application to the target area. In some situations, the user of ,the biological formulation may be satisfied to use just an aqueous emulsion of the E.C., for any of the above-mentioned utilities, including herbicidal formulations. Alternatively, and of growing practice, the user of a biological formulation may desire to apply a liquid fertilizer simultaneously with and from the same container holding a herbicide, etc. How-ever, a distinct limitation upon the use of various EC's is that whereas an EC may be suitably compatible with water, it is incompatible with liquid fertilizers and vice-versa; said incompatibility being manifested by phase separation of components usually within a short period of time. Even when a herbicidal EC is specifically designed for compatibility with a liquid fertilizer, such compatibility can be short-lived. For example, in U.S. Patent 3,~36,626, the biocidal toxicant fertilizer composition designed for prolonged ~1 ~'i`;g ~
1 1 7~5~
The invention herein pertains to the field of emulsifier compositions and emulsifiable concentrate formulations having biological activity, e.g., as herbicides, and having as the active ingredient thereof at least one compound selected from the group consisting of substituted acetanilides, thio-carbamates and anilines.
The prior art relative to emulsifiable concentrate (EC) formulations includes a wide variety of active ingredients and emulsifier/surfactant systems therefor. Such EC's are suitable for a variety of biological and agricultural utilities, both plant and animal, e.g., on soil or plants as herbicides, her-bicidal antidotes, plant growth regulators, nematocides, bac-tericides, fungicides, insecticides, soil fumigants, etc.
In practice, the EC containing the biologically-active ingredient is diluted in water and/or liquid fertilizer before application to the target area. In some situations, the user of ,the biological formulation may be satisfied to use just an aqueous emulsion of the E.C., for any of the above-mentioned utilities, including herbicidal formulations. Alternatively, and of growing practice, the user of a biological formulation may desire to apply a liquid fertilizer simultaneously with and from the same container holding a herbicide, etc. How-ever, a distinct limitation upon the use of various EC's is that whereas an EC may be suitably compatible with water, it is incompatible with liquid fertilizers and vice-versa; said incompatibility being manifested by phase separation of components usually within a short period of time. Even when a herbicidal EC is specifically designed for compatibility with a liquid fertilizer, such compatibility can be short-lived. For example, in U.S. Patent 3,~36,626, the biocidal toxicant fertilizer composition designed for prolonged ~1 ~'i`;g ~
1 1 7~5~
-2- AG-1214 stability only had a useful life 1l ... for perlods of the order of at least hours." The instability of the herbicide-fertilizer mixture and phase separation results in non-uniform distribution of herbicide and fertilizer, hence erratic and incomplete weed control and crop feeding, in addition to apparatus and equipment problems and failures. It then requires continuous agitation of the herbicide-fertilizer mixture to keep the compone~ts in a homogeneous state, a practice both cumbersome, expensive and not always practicable.
In further attempts to obtain stable compositions of bio-logically active components, with or without fertilizer mater-ials, various workers in the prior art have resorted to emulsi-fier-surfactant systems based upon a balancing of the hydrophilic and lipophilic (i.e., "HLB" balance) components of the system;
see e.g., U.S. Pat. Nos. 3,236,626, 3,986,362 and 4,080,191.
A further problem associated with many prior art EC's is the necessity to use a stabilizer for various components there-in. As an examPle, heretofore it has been necessary to use a stabilizer, or combination of stabilizers to stabilize herbi-cidal formulations of such acetanilides as alachlor, i.e., 2i,6'-diethyl-N-(methoxymethyl)-2-chloroacetanilide.
Yet another problem in the use of prior art formulations mixed with fertilizers is the corrosion problem. Containers used by farmers to tank mix herbicides and fertilizers are com-25 monly made of mild steel, zinc or aluminum or alloys containingthese elements. These containers are subject to corrosion from water and acidic components of the fertilizer and aqueous herbi-cidal formulations.
It is, therefore, the primary object of this invention to 30 provide EC's of biologically-active formulations which are phy-sically compatible with both water and liquid fertilizers.
Another object of this invention is to provide an emulsi-fier system for biologically-active EC's which simultaneously provides emulsification, stabilization and anti-corrosion 35 properties.
A particular object and advantage of this invention is the provision of an EC of herbicidally-active compounds which can be used equally well in either aqueous systems or liquid fertilizer systems which are physically and homogeneously stable for a per-~ 3 ~ 5 ~ -iod of weeks, as opposed to hours as presently known.
~et another object of this invention is the pro-vision of a stabilized EC which is not dependent upon any particular H~B characteristic or parameter. Thus, for a fixed ratio of surfactants, the EC'S of this invention are stable and compatible with all waters ~i.e., soft, WHO and hard) and with fluid fertilizers, whereas prior art EC's using conventional anionic and nonionic surfactants must be present in matched pairs to balance performance in each water and fluid fertilizer system.
A further advantage of the EC's of this invention is the ability to load high concentrations, i.e., from 4 to 7 lbs/gal or more of active ingredient, as opposed to some prior art EC's, which may contain only 2 or 3 lbs/gal of active ingredient. The advantages of these high-yield EC's are well known to the art and include, e.g., a reduced volume of formulated product, which in turn, results in a reduction in the number, handling, transportation and storage of containers for the herbicides.
These and other objects will become apparent from the description below.
This invention relates in its various aspects to an emulsifier composition comprising, in combination:
(1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8 20 aliphatic alcohols, and (2) one or more amines selected from the group ~ consisting of:
(a) fatty tertiary amines of the formula RlN (~) 2; (b) fatty amine oxides of the formula O
R N(CH2CH2OH)2; (c) beta-amines of the formula H3CCH(NH2)R;
(d) amido-bridged tertiary amines of the formula R CON (CH2)3N-(~)2; (e) ethoxylated tertiary amines of the formulae:
~i) R N (CH2CH20H)2 and 2CH2 ) NR (CH2 ) 3N (CH2CH2OH) 2; and (f) polypropoxylated low molecular weight tertiary amines;
where R is a Cl 5 alkyl radical and Rl is a C8 18 aliphatic .2 , ~ ~
~ 17~6 hydrocarbon radical; and wherein the weight ratio of components (1) to (2~ is within the range of about 1:1 to about 10:1.
Another aspect of the invention relates to an emulsifier concentrate comprising the above emulsifier composi-tion and at least one biologically-active compound selected from the group consisting of substituted acetanilides, thio-carbamates and anilines.
A solvent can also be included in the above concentrate when necessary or desired.
In the following, and for ease of reference, component (A) will designate the biologically-active compound; component (B) the emulsifier composition described above; and component (C) the solvent.
Particularly preferred herbicidal emulsifiable concen-trates are those wherein component (A) is present in an amount within the range of about 5.0 - 98.0%, preferably within the range of about 10.0 - 50.0~ by weight, component (B) is present in an amount within the range of about 2.0 - 50.0~ by weight, preferably from 3.0 to 15.0~, and the balance component (C)O
The weight ratio of components (B)(l) to ~B)(2) will vary somewhat in EC's having different component (A) members, but in general will be within the range of about 1:1 to 10 preferably from about 4:1 to 6:1.
The solvent component (C) may be either a straight solvent or mixed solvent, no criticality be;ng placed -thereon.
In another aspect, this invention rela-tes to EC's of the above description wherein the bio]ogically-active component is effective under appropriate conditions and concentrations as a herbicide, a non-phytoxic plant growth regulant, herbi-cidal antidote, insecticide, nematocide, fungicide, bacteri-cide, or other biologically-effective utility. Although of very broad purview and contemplation, the presently preferred biologically-active compounds are substituted 2-haloacetanilides, carbamates and anilines. of particular interest as representa-tive compounds of these classes are specifically mentioned in their embodiments as herbicidal compounds alachlor, butachlor, acetochlor, metolachlor, triallate, trifluralin, EPTC and butylate, with and without an antidote, e.g., N'N-diallyl-2,2-1 3~8~
dichloroacetamide, and homologs, isomers, analogs and other structurally related compounds having herbicidal activity.
In its most preferred aspect, the present invention relates to herbicidal EC's of the above description wherein the herbicidally-active ingredient is alachlor and the pre-ferred emulsifier system comprises as the phosphate ester a mixture of mono- and diphosphate esters of ethoxylated nonylphenol and the preferred amine is an ethoxylated coconut oil amine.
Finally, the invention in practical application relates to physically s-table emulsions of biologically-active, e.g., herbicidal, EC's as defined above in water and in liquid fertilizer compositions.
As indicated in the summary of the invention, it has been discovered that broad spectrum performance with respect to stabilization, spontaneity and corrosion inhibition in a wide variety of emulsifiable concentrates (EC's) has been achieved by means of a unique emulsification system which is equally effective in all waters and in liquid fertilizers.
The EC's herein comprise a complexed combination of the following components:
(A) at least one biologically-active compound selected from the group consisting of substituted acetanilides, thio-carbamates and anilines;
(B) an emulsifier system comprising:
(1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8 20 aliphatic alcohols and (2) an amine selected from the group consisting of:
(a) fatty tertiary amines of the formula R N(R~2 (b) fatty amine oxides of the formula o R N(CH2CH2OH)2;
(c) beta-amines of the formula H3CCH(NH2)Rl;
(d) amido-bridged tertiary amines of the formula RlCON(CH2)3N(R)2;
.,.~ . .
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(e) ethoxylated tertiary amines of the formulae (i) R -N(CH2CH2OH)2 and ( ~2CH2)NR (~H2)3N(CH2cH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines;
wherein R is a Cl 5 alkyl radical and Rl is a C8 18 aliphatic hydrocarbon radical; and (c) a solvent when necessary or desired.
With further respect to the above emulsification system, suitable phosphate esters of ethoxylated alcohols, both aromatic and aliphatic (component (B)(l)) are prepared by reacting P2O5 with a variety of non-ionic surface active agents as described in full detail in U. S. Patent 3,004,056.
Representatives of such phosphate esters are commercially available, e.g., from GAF Corporation, under its GAFAC trade-mark series, e.g., GAFAC RE-610, GAFAC RM-510, GAFAC PE-510, etc.; these surfactants being defined as free acid of complex organic phosphate of aromatic or aliphatic hydro-phobe base.
With further respect to the amine components (B)(2), preferred members of the (a) subclass are those fatty tertiary amines wherein R is a C12H25 or C18H37 alkyl radical; a preferred subclass (b) member is fatty amine oxides wherein R is a C12H25 radical; preferred beta-amines of subclass (c) are those wherein R is an aliphatic C8 18 aliphatic hydro-carbon chain which may be saturated or unsaturated; preferred subclass (d) amido-bridged tertiary amines are those wherein Rl is a fatty radical (chiefly C12) derived from coconut oil or from castor oil (chiefly rincinoleic acid)i preferred ethoxylated tertiary amines of subclass (2)(e)(ii) above are those wherein Rl is tallow, and for subclass (2)(e)(i) Rl is coconut oil or tallow and preferred subclass (f) members are the commercially available (Witco) amines identified as OSA-75 and OSA-120.
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It has been found that the above emulsifier system is suitable across a number of different classes of chemical compounds, thus suggesting broad spectrum applicability.
In preferred embodiments, the emulsifier system herein is useful in current commercial herbicides. Tests have shown that representative component (A) members include 2-haloacetani-lides within the formula o XCH2C \ ~ R2 N
~(R )n wherein X is chlorine, bromine or iodine, n is an integer from 0-5 and R2 and R3 represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxyalkyl or polyalkoxyalkyl groups having up to 18 carbon atoms, cycloalkyl, cycloalkyloxy or cycloalkylalkyl groups having up to 10 carbon atoms r aralkyl or alkaryl groups having up to 18 carbon atoms or o, S or N-heterocycyl or heterocycyalkyl radicals having up to 7 ring members, or said R2 and R3 members substituted with alkyl, alkenyl, alkynyl, halo, nitro, cyano, hydroxy, CF3, amino, mono- and di-alkyl amino groups. The preferred R2 and R3 aliphatic members are those having up to 8 carbon atoms and preferred aromatic members having up to 10 carbon atoms. Of still more preferred interest are 2-haloacetanilides wherein R2 is an alkyl or alkoxyalkyl radical and R3 members are hydrogen, alkyl, alkoxy and/or alkoxyalkyl radicals, and particularly, alkyl, alkoxy or alkoxyalkyl substitution in at least one, preferably both, ortho positions. Of primary importance are the specific members 2',6'-diethyl-N-(methoxymeth~1)-2-chloro-acetanilide (common name "alachlor"); 2'6'-diethyl-N-(butoxy-methyl)-2-chloroacetanilide (common name "butachlor"); 2'-ethyl-6'-methyl-N-(ethoxymethyl)-2-chloroacetanilide (common name "acetochlor"); and 2'-ethyl-6'-methyl-N-(l-methoxyprop-2-yl)-2-chloroacetanilide (common name "metolachlor").
~ 1 7~85~
Another ciass of component (A) members are thio-carbamates having the formula O
R4SC-N(R )2 wherein R4 is a C1 4 alkyl or di- or trichloroallyl radical and R5 is -a Cl 4 alkyl, preferably n- or i-propyl and i-butyl.
Preferred members within the above class are S-2,3,3,-tri-chloroallyl diisopropylthiocarbamate (common name '^triallate"), S-ethyl diisobutylthiocarbamate (common name "butylate") and S-ethyl di-n-propylthiocarbamate (common name "EPTC").
Yet another class of component (A) members in the above emulsification system are substituted 2,6-dinitro-4-trifluoromethylanilines of the formula (R6)2 N
2 ~ NO2 wherein R6 is a C] 4 lowerlalkyl member, preferably, n-propyl.
This class is represented by the compound 2,6-dinitro-4-tri-fluoromethylani:Line (common name "trifluralin").
~ solvent (component C) may be used to solubilize any component, especially component (A), which is water-insoluble or normally insoluble at ambient temperatures. Exemplary solvents include aromatic, paraffinic or naphthenic hydrocarbon solvents or blends thereof, such as benzene, toluene, alkylated naphthalenes, cyclohexane, the xylenes and ~erosene, haloben-zenes, e.g., monochlorobenzene, halogenated alkanes, etc.
These and other organic solvents sold under tradenamesr such as Tenneco T-400 or T-500-100, which are mixtures of aromatic hydrocarbons in the C8-Cg range, including the alkylbenzenes.
The selection of a solvent is not critical to this invention, but is subject to normal considerations of safety, environmental impact considerations and physical and cost limitations.
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g In addition to the foregoing ingredients, other con-ventional additaments may be included, such as defoamers, e.g., silicone polymers, commercially available, e.g., as Mazu DF-lOOs*, odorants and dyes, as will be understood by those skilled in the art.
In broad purview, the EC's of this invention contain biologically-active compounds (component (A~ members) exempli-fied above and are suitable for use in any biological utility of which said compounds are effective. The primary aspect of this invention is the emulsifier system described above as component (B); the particular utility is secondary, being dictated by the properties and characteristics of active ingredient(s) in the EC. Thus, EC's herein find utility in such biological areas as herbicides, herbicidal antidotes, plant growth regulators, insecticides, fungicides, nematocides, bactericides, soil fumigants, etc. However, of primary interest and application herein, the present EC's are equally compatible in all waters and fluid fertilizers making them highly desirable vehicles for plant and soil treatment, e.g., in herbicidal, herbicide/antidote and plant growth regulator formulations.
Of further interest herein is the provision of herbici-dal and herbicide/antidote EC's which are of broad commercial - application and which contain as the active ingredient thereof the above preferred compounds identified by chemical nomen-clature and common name. While particularly useful in many crop/weed regimes, the above herbicide formulations have _ particular limitations which are recognized. Thus, alachlor, if used alone is somewhat injurious to sorghum; butylate some-what injurious to field corn and butachlor to rice in some situations. Consequently, herbicidal antidotes or safeners have been developed to reduce crop injury by the herbicide.
For example, it has been found that suitable antidotes for alachlor, butachlor, acetochlor or metolachlor in sorghum are ethyl 2-chloro-4-trifluoromethyl-5-thiazolecarboxylate and benzyl-2-chloro-4-trifluoromethyl-5-thiazolecarboxylate. An effective antidote for butachlor in rice is 3-(2'5'-dimethoxy-phenacyl)-phthalate or ethyl 5-(2,4-dichlorophenyl)-~-isoxazolecarboxylate. An effective antidote for metolachlor * Trademark I ~ 7~s5~
- 9a -in corn is O~-(cyanomethoxyamino)-benzacetonitrile and an effective antidote for EPTC and butylate in field corn is N,N-diallyl-2,2-dichloroacetamide.
The herbicidal ~C'S herein are very versatile in use. Thus, where it is desired to apply a herbicide either in straight wa~er base or in a fluid fertilizer solution, the EC's herein are equally suitable, such EC's are un~nown to the prior art. In current practice, distinct EC's must be provided for use in water based formulations and in fluid fertilizer-based formulations, because neither formula-tion is compatible with or physically sta~le in the other base. Moreover, the prior art EC's generally require added stabilizers to retard degradation of the EC.
The preferred EC's herein are those wherein component (A) is present in a herbicidally effective amount within the range of about 5.0-98.0% by weight, preferably 5.0-50%, com-ponent (B) is present in an amount within the range of about 2.0-50.0% by weight, preferably from 3.0 to 15% by weight and the balance component (C); the weight ratio of components (B) (1) to (B)(2) is within the range of about 2:1 to 10:1. The preferred component (B)(l) member is a mixture of mono- and di-phosphate esters of ethoxylated nonylphenol and component (B) lo 1 1 7~85~ ~G-1214 (2) is an ethoxylated tertiary amine of the formula RlN(C~2CH2-OH)2 wherein Rl is a C8 18 aliphatic hydrocarbon radical, the weight ratio of components (B)(l) to (B)(2) be1ng within the range of about 4.0:1.0 to 6.0:1,0. A more preferred component S (B)(l) member is a free acid of a complex organic phosphate ester of aromatic or aliphatic hydrophobe base and a prefexred component (B)(2) member is an ethoxylated tertiary amine derived frGm oxx~t oil, ~an oil, cott~d oil, ~m oil or tallow, exRmplified by o~n~rcially-available surfactants such as Ethomeen*C/12, C/15, C~20, C/25, S/12, S/15, S/20, T/12, T/13, T/20, etc. Preferred emLlsifiable concentrates herQ~ are ~x~e wh~n CampOn~lt (A) is selected ~xm the qroup consisting of alachlor, but~or, acet~or, metolachlor, triallate, trifluralin, and but,vLate.
Preferred EC's according to this invention are described in Examples 1-8 below.
Example 1 In this example, a 4 lb/gal (0.48 kg/l) EC formulation of alachlor is described.
Ingredients Weight Percent Alachlor (91% assay) 49.63 GAFAC RE-610 4.125 Ethomeen*C/12 0.875 Mazu DF-lOOs* 0.010 Methyl violet 0.017 Solvent (monochloro-benzene and T-400) 45.343 100.00 Example 2 This example describes a 5 lb/gal (0.6 kg/1) EC
formulation of butachlor.
In~redients Weight Percent ~utachlor (89~ assay~ 65.46 GAFAC RM 510 4,125 Ethomeen*C/12 0.375 Methyl violet Q.017 Mazu DF-lOOs* 0.01 T500-100 29.~13 100 . 00 * Trademarks . _ . ,, . _ _ ~ 1 1 7~85~ AG-1214 Example 3 This ex~mple describes a 4 lb/gal EC formulation of acetochlor.
Ingredients Weight Percent Acetochlor (93% assay) - 51.59 GAFAC RE-610 8.25 Ethomeen C/12 1.75 T-500-100 38.41 i00 . 00 Example 4 This example describes a 4 lb/gal EC formulatiorL of metolachlor.
Inqredients Weight Percent Metolachlor (93.77%) 48.19 GAFAC RE-610 2.00 GAFAC PE-510 2.00 Ethomeen C/12 1.00 Solvent (T400 and monochlorobenzene) 46.81 Example 5 A 4 lb/gal EC formulation of triallate is described in this example.
Ingredients Weight Percent Triallate (91~) 43.27 GAFAC RE-610 1.80 GAFAC 2E-510 2.70 Ethomeen C/12 0.50 Xylene 51.73 100 . 00 Example 6 This example describes a 7 lb/gal (0.84 kg/l) EC
formulation o~ butylate, ~ ~7~8~
IngredientsWeight Percent Butylate (100%)90 00 GAFAC RE-610 3.60 GAFAC PE-510 5.40 Ethomeen* C/121.00 100 . 00 Example 7 This example describes a 7 lb/gal EC of butylate containing as an antidote the compound N,N-diallyl-2,2-dichloroacetamide.
IngredientsWeight Percent Butylate (100%)85.83 Antidote 4.17 GAFAC RE-610 3.60 Ethomeen* C/121.00 100 . 00 Example 8 This example illustrates a 4 lb/gal EC formula-tion of trifluralin.
IngredientsWeight Percent Trifluralin (95%)48.32 Flo MO6NP* 4.25 Ethomeen* C/120.75 Solvent (T 400)46.68 100 . 00 In order to demonstrate the compatibility and stability of the EC's of this invention in emulsions of water and fluid fertilizers, a series of tests were run using a variety of emulsification systems according to this invention. In these tests, the water used conformed to World Health Organization (WHO) standard water, defined as a combination hard water of 342 ppm hardness (0.304 g.
CaC12, anhydrous or 0.4027 g. cacl2.2H2o~ plus 0.139 g. MgC12.6H2O plus distilled water to make 1 liter). The fertilizer solution used was a 28% nitrogen * Trademarks 8~
solution fer~ilizer made up by dissolving 496.4 g. of NH4NO3 and 396.8 g. of urea in 386.56 g. distilled water to make a one liter solution.
In conducting the stability tests in the fluid fertilizer solution approximately 1.6 ml of the EC is added to 40 mls of fertilizer solution in a suitable container which is then stoppered and vigorously shaken. Volume percent separation of oil is observed and determined after 15 minutes.
In conducting the water tests, both for spontaniety ("bloom") and stability, a measured volume of the EC is poured into the water in a suitable container, e.g., a Nessler tube, via a funnel and observing the degree of spontaneous emulsifi-cation. After the emulsion cloud reaches the bottom of the tube, the tube is stoppered, inverted 15 times and observed after 15 minutes and/or one hour for any separation. This test is usually run at a dilution rate of 1:19, e.g., 5 ml of EC in 95 ml water. The criteria for judging spontaniety is as follows: "Perfect" - a thick emulsion clou~ descending to the bottom of the tube without separation of any type; "Good" -thin "bloom" or cloud with no separation or thick cloud withminor separation such as emulsion trails at 1" (2.5 cm) or less from the bottom of the tube, "flc,wering", etc., and "Poor" -emulsion cloud containing oil droplets with oil separation from cloud above 1" from bottom of the tube. The criteria for measuring stability is the formation of 2 ml or less cream and no oil in WHO water and 5 ml or less cream and no oil in soft and hard waters; "soft water" is defined as having 114 ppm hardness prepared by diluting 1 part WHO hard water (defined above) with 2 parts of distilled water, and "hard water" is defined as 1000 ppm all calciu~ (prepared by dissolving 1.4691 g. of 100% CaC12~2~2O in distilled water and diluting to 1 liter) = 1000 ppm CaCO3 The volume separation in mls is converted by formula into volume percent separation.
In ~able 1 data is presented for tests at 25C of a plurality of emulsification systems for alachlor as the active I J ~85~
ingredient (component (A~) in the above EC description. In these tests, the phosphate ester component ((B)(l) above) was a mixture of mono- and di-phosphate esters of ethoxylated nonylphenol and the amine component ((B)(l)(a)-(f)) in the S above EC description is identified as in Examples 9-20. All the surfactants used herein, both phosphate esters and amines are available from commercial surfactant suppliers.
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As will be apparent from the stability data in Table 1, the EC's according to this invention were all perfectly stable 15 minutes after emulsification. The significance of this stability data will be more appreciated by reference to the stability data for commercial EC's set forth in Table 2 below according to test procedures described above.
In Table 2, under the first column are listed various EC's; these EC's were tested i.n waters of various hardness ranging from soft through WHO to hard waters indicated under the second column and in liquid fertilizer solutions of 28%
nitrogen ("LF" in second column~. The properties of the tested EC's are shown under the columns entitled "Spontaneity" for water and "Stabil.ity" in water and liquid fertilizer; the data for the invention EC's is listed side-by-side that for EC's now in commercial use. ~s stated earlier herein, since EC
formulations of a particular composition which are stable in water are unstable in liquid fertilizers and vice-versa, the result is a necessity to resort to two distinct EC's dif-ferently formulated in order to obtain maximum stability in the different emulsion bases. Thus, in Table 2, Formulation A is a commercial "water-grade" EC containing alachlor as the active ingredient and Eormulation B is a differently-formulated commercial alachlor EC for use in liquid fertilizers.
Similarly, Formulation C is a water-grade butachlor EC and Formulati.on D is a fertilizer-grade butachlor EC. The emulsification systems of the commercial EC's are proprietary to the manufacturers, but are of no significance for purposes of these tests other than to show the overall inferiority thereof relative to the unique emulsification system of this invention.
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In further attempts to obtain stable compositions of bio-logically active components, with or without fertilizer mater-ials, various workers in the prior art have resorted to emulsi-fier-surfactant systems based upon a balancing of the hydrophilic and lipophilic (i.e., "HLB" balance) components of the system;
see e.g., U.S. Pat. Nos. 3,236,626, 3,986,362 and 4,080,191.
A further problem associated with many prior art EC's is the necessity to use a stabilizer for various components there-in. As an examPle, heretofore it has been necessary to use a stabilizer, or combination of stabilizers to stabilize herbi-cidal formulations of such acetanilides as alachlor, i.e., 2i,6'-diethyl-N-(methoxymethyl)-2-chloroacetanilide.
Yet another problem in the use of prior art formulations mixed with fertilizers is the corrosion problem. Containers used by farmers to tank mix herbicides and fertilizers are com-25 monly made of mild steel, zinc or aluminum or alloys containingthese elements. These containers are subject to corrosion from water and acidic components of the fertilizer and aqueous herbi-cidal formulations.
It is, therefore, the primary object of this invention to 30 provide EC's of biologically-active formulations which are phy-sically compatible with both water and liquid fertilizers.
Another object of this invention is to provide an emulsi-fier system for biologically-active EC's which simultaneously provides emulsification, stabilization and anti-corrosion 35 properties.
A particular object and advantage of this invention is the provision of an EC of herbicidally-active compounds which can be used equally well in either aqueous systems or liquid fertilizer systems which are physically and homogeneously stable for a per-~ 3 ~ 5 ~ -iod of weeks, as opposed to hours as presently known.
~et another object of this invention is the pro-vision of a stabilized EC which is not dependent upon any particular H~B characteristic or parameter. Thus, for a fixed ratio of surfactants, the EC'S of this invention are stable and compatible with all waters ~i.e., soft, WHO and hard) and with fluid fertilizers, whereas prior art EC's using conventional anionic and nonionic surfactants must be present in matched pairs to balance performance in each water and fluid fertilizer system.
A further advantage of the EC's of this invention is the ability to load high concentrations, i.e., from 4 to 7 lbs/gal or more of active ingredient, as opposed to some prior art EC's, which may contain only 2 or 3 lbs/gal of active ingredient. The advantages of these high-yield EC's are well known to the art and include, e.g., a reduced volume of formulated product, which in turn, results in a reduction in the number, handling, transportation and storage of containers for the herbicides.
These and other objects will become apparent from the description below.
This invention relates in its various aspects to an emulsifier composition comprising, in combination:
(1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8 20 aliphatic alcohols, and (2) one or more amines selected from the group ~ consisting of:
(a) fatty tertiary amines of the formula RlN (~) 2; (b) fatty amine oxides of the formula O
R N(CH2CH2OH)2; (c) beta-amines of the formula H3CCH(NH2)R;
(d) amido-bridged tertiary amines of the formula R CON (CH2)3N-(~)2; (e) ethoxylated tertiary amines of the formulae:
~i) R N (CH2CH20H)2 and 2CH2 ) NR (CH2 ) 3N (CH2CH2OH) 2; and (f) polypropoxylated low molecular weight tertiary amines;
where R is a Cl 5 alkyl radical and Rl is a C8 18 aliphatic .2 , ~ ~
~ 17~6 hydrocarbon radical; and wherein the weight ratio of components (1) to (2~ is within the range of about 1:1 to about 10:1.
Another aspect of the invention relates to an emulsifier concentrate comprising the above emulsifier composi-tion and at least one biologically-active compound selected from the group consisting of substituted acetanilides, thio-carbamates and anilines.
A solvent can also be included in the above concentrate when necessary or desired.
In the following, and for ease of reference, component (A) will designate the biologically-active compound; component (B) the emulsifier composition described above; and component (C) the solvent.
Particularly preferred herbicidal emulsifiable concen-trates are those wherein component (A) is present in an amount within the range of about 5.0 - 98.0%, preferably within the range of about 10.0 - 50.0~ by weight, component (B) is present in an amount within the range of about 2.0 - 50.0~ by weight, preferably from 3.0 to 15.0~, and the balance component (C)O
The weight ratio of components (B)(l) to ~B)(2) will vary somewhat in EC's having different component (A) members, but in general will be within the range of about 1:1 to 10 preferably from about 4:1 to 6:1.
The solvent component (C) may be either a straight solvent or mixed solvent, no criticality be;ng placed -thereon.
In another aspect, this invention rela-tes to EC's of the above description wherein the bio]ogically-active component is effective under appropriate conditions and concentrations as a herbicide, a non-phytoxic plant growth regulant, herbi-cidal antidote, insecticide, nematocide, fungicide, bacteri-cide, or other biologically-effective utility. Although of very broad purview and contemplation, the presently preferred biologically-active compounds are substituted 2-haloacetanilides, carbamates and anilines. of particular interest as representa-tive compounds of these classes are specifically mentioned in their embodiments as herbicidal compounds alachlor, butachlor, acetochlor, metolachlor, triallate, trifluralin, EPTC and butylate, with and without an antidote, e.g., N'N-diallyl-2,2-1 3~8~
dichloroacetamide, and homologs, isomers, analogs and other structurally related compounds having herbicidal activity.
In its most preferred aspect, the present invention relates to herbicidal EC's of the above description wherein the herbicidally-active ingredient is alachlor and the pre-ferred emulsifier system comprises as the phosphate ester a mixture of mono- and diphosphate esters of ethoxylated nonylphenol and the preferred amine is an ethoxylated coconut oil amine.
Finally, the invention in practical application relates to physically s-table emulsions of biologically-active, e.g., herbicidal, EC's as defined above in water and in liquid fertilizer compositions.
As indicated in the summary of the invention, it has been discovered that broad spectrum performance with respect to stabilization, spontaneity and corrosion inhibition in a wide variety of emulsifiable concentrates (EC's) has been achieved by means of a unique emulsification system which is equally effective in all waters and in liquid fertilizers.
The EC's herein comprise a complexed combination of the following components:
(A) at least one biologically-active compound selected from the group consisting of substituted acetanilides, thio-carbamates and anilines;
(B) an emulsifier system comprising:
(1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8 20 aliphatic alcohols and (2) an amine selected from the group consisting of:
(a) fatty tertiary amines of the formula R N(R~2 (b) fatty amine oxides of the formula o R N(CH2CH2OH)2;
(c) beta-amines of the formula H3CCH(NH2)Rl;
(d) amido-bridged tertiary amines of the formula RlCON(CH2)3N(R)2;
.,.~ . .
~ ~ 7 ~
(e) ethoxylated tertiary amines of the formulae (i) R -N(CH2CH2OH)2 and ( ~2CH2)NR (~H2)3N(CH2cH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines;
wherein R is a Cl 5 alkyl radical and Rl is a C8 18 aliphatic hydrocarbon radical; and (c) a solvent when necessary or desired.
With further respect to the above emulsification system, suitable phosphate esters of ethoxylated alcohols, both aromatic and aliphatic (component (B)(l)) are prepared by reacting P2O5 with a variety of non-ionic surface active agents as described in full detail in U. S. Patent 3,004,056.
Representatives of such phosphate esters are commercially available, e.g., from GAF Corporation, under its GAFAC trade-mark series, e.g., GAFAC RE-610, GAFAC RM-510, GAFAC PE-510, etc.; these surfactants being defined as free acid of complex organic phosphate of aromatic or aliphatic hydro-phobe base.
With further respect to the amine components (B)(2), preferred members of the (a) subclass are those fatty tertiary amines wherein R is a C12H25 or C18H37 alkyl radical; a preferred subclass (b) member is fatty amine oxides wherein R is a C12H25 radical; preferred beta-amines of subclass (c) are those wherein R is an aliphatic C8 18 aliphatic hydro-carbon chain which may be saturated or unsaturated; preferred subclass (d) amido-bridged tertiary amines are those wherein Rl is a fatty radical (chiefly C12) derived from coconut oil or from castor oil (chiefly rincinoleic acid)i preferred ethoxylated tertiary amines of subclass (2)(e)(ii) above are those wherein Rl is tallow, and for subclass (2)(e)(i) Rl is coconut oil or tallow and preferred subclass (f) members are the commercially available (Witco) amines identified as OSA-75 and OSA-120.
~7~
It has been found that the above emulsifier system is suitable across a number of different classes of chemical compounds, thus suggesting broad spectrum applicability.
In preferred embodiments, the emulsifier system herein is useful in current commercial herbicides. Tests have shown that representative component (A) members include 2-haloacetani-lides within the formula o XCH2C \ ~ R2 N
~(R )n wherein X is chlorine, bromine or iodine, n is an integer from 0-5 and R2 and R3 represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxyalkyl or polyalkoxyalkyl groups having up to 18 carbon atoms, cycloalkyl, cycloalkyloxy or cycloalkylalkyl groups having up to 10 carbon atoms r aralkyl or alkaryl groups having up to 18 carbon atoms or o, S or N-heterocycyl or heterocycyalkyl radicals having up to 7 ring members, or said R2 and R3 members substituted with alkyl, alkenyl, alkynyl, halo, nitro, cyano, hydroxy, CF3, amino, mono- and di-alkyl amino groups. The preferred R2 and R3 aliphatic members are those having up to 8 carbon atoms and preferred aromatic members having up to 10 carbon atoms. Of still more preferred interest are 2-haloacetanilides wherein R2 is an alkyl or alkoxyalkyl radical and R3 members are hydrogen, alkyl, alkoxy and/or alkoxyalkyl radicals, and particularly, alkyl, alkoxy or alkoxyalkyl substitution in at least one, preferably both, ortho positions. Of primary importance are the specific members 2',6'-diethyl-N-(methoxymeth~1)-2-chloro-acetanilide (common name "alachlor"); 2'6'-diethyl-N-(butoxy-methyl)-2-chloroacetanilide (common name "butachlor"); 2'-ethyl-6'-methyl-N-(ethoxymethyl)-2-chloroacetanilide (common name "acetochlor"); and 2'-ethyl-6'-methyl-N-(l-methoxyprop-2-yl)-2-chloroacetanilide (common name "metolachlor").
~ 1 7~85~
Another ciass of component (A) members are thio-carbamates having the formula O
R4SC-N(R )2 wherein R4 is a C1 4 alkyl or di- or trichloroallyl radical and R5 is -a Cl 4 alkyl, preferably n- or i-propyl and i-butyl.
Preferred members within the above class are S-2,3,3,-tri-chloroallyl diisopropylthiocarbamate (common name '^triallate"), S-ethyl diisobutylthiocarbamate (common name "butylate") and S-ethyl di-n-propylthiocarbamate (common name "EPTC").
Yet another class of component (A) members in the above emulsification system are substituted 2,6-dinitro-4-trifluoromethylanilines of the formula (R6)2 N
2 ~ NO2 wherein R6 is a C] 4 lowerlalkyl member, preferably, n-propyl.
This class is represented by the compound 2,6-dinitro-4-tri-fluoromethylani:Line (common name "trifluralin").
~ solvent (component C) may be used to solubilize any component, especially component (A), which is water-insoluble or normally insoluble at ambient temperatures. Exemplary solvents include aromatic, paraffinic or naphthenic hydrocarbon solvents or blends thereof, such as benzene, toluene, alkylated naphthalenes, cyclohexane, the xylenes and ~erosene, haloben-zenes, e.g., monochlorobenzene, halogenated alkanes, etc.
These and other organic solvents sold under tradenamesr such as Tenneco T-400 or T-500-100, which are mixtures of aromatic hydrocarbons in the C8-Cg range, including the alkylbenzenes.
The selection of a solvent is not critical to this invention, but is subject to normal considerations of safety, environmental impact considerations and physical and cost limitations.
~ ~ 7~85~
g In addition to the foregoing ingredients, other con-ventional additaments may be included, such as defoamers, e.g., silicone polymers, commercially available, e.g., as Mazu DF-lOOs*, odorants and dyes, as will be understood by those skilled in the art.
In broad purview, the EC's of this invention contain biologically-active compounds (component (A~ members) exempli-fied above and are suitable for use in any biological utility of which said compounds are effective. The primary aspect of this invention is the emulsifier system described above as component (B); the particular utility is secondary, being dictated by the properties and characteristics of active ingredient(s) in the EC. Thus, EC's herein find utility in such biological areas as herbicides, herbicidal antidotes, plant growth regulators, insecticides, fungicides, nematocides, bactericides, soil fumigants, etc. However, of primary interest and application herein, the present EC's are equally compatible in all waters and fluid fertilizers making them highly desirable vehicles for plant and soil treatment, e.g., in herbicidal, herbicide/antidote and plant growth regulator formulations.
Of further interest herein is the provision of herbici-dal and herbicide/antidote EC's which are of broad commercial - application and which contain as the active ingredient thereof the above preferred compounds identified by chemical nomen-clature and common name. While particularly useful in many crop/weed regimes, the above herbicide formulations have _ particular limitations which are recognized. Thus, alachlor, if used alone is somewhat injurious to sorghum; butylate some-what injurious to field corn and butachlor to rice in some situations. Consequently, herbicidal antidotes or safeners have been developed to reduce crop injury by the herbicide.
For example, it has been found that suitable antidotes for alachlor, butachlor, acetochlor or metolachlor in sorghum are ethyl 2-chloro-4-trifluoromethyl-5-thiazolecarboxylate and benzyl-2-chloro-4-trifluoromethyl-5-thiazolecarboxylate. An effective antidote for butachlor in rice is 3-(2'5'-dimethoxy-phenacyl)-phthalate or ethyl 5-(2,4-dichlorophenyl)-~-isoxazolecarboxylate. An effective antidote for metolachlor * Trademark I ~ 7~s5~
- 9a -in corn is O~-(cyanomethoxyamino)-benzacetonitrile and an effective antidote for EPTC and butylate in field corn is N,N-diallyl-2,2-dichloroacetamide.
The herbicidal ~C'S herein are very versatile in use. Thus, where it is desired to apply a herbicide either in straight wa~er base or in a fluid fertilizer solution, the EC's herein are equally suitable, such EC's are un~nown to the prior art. In current practice, distinct EC's must be provided for use in water based formulations and in fluid fertilizer-based formulations, because neither formula-tion is compatible with or physically sta~le in the other base. Moreover, the prior art EC's generally require added stabilizers to retard degradation of the EC.
The preferred EC's herein are those wherein component (A) is present in a herbicidally effective amount within the range of about 5.0-98.0% by weight, preferably 5.0-50%, com-ponent (B) is present in an amount within the range of about 2.0-50.0% by weight, preferably from 3.0 to 15% by weight and the balance component (C); the weight ratio of components (B) (1) to (B)(2) is within the range of about 2:1 to 10:1. The preferred component (B)(l) member is a mixture of mono- and di-phosphate esters of ethoxylated nonylphenol and component (B) lo 1 1 7~85~ ~G-1214 (2) is an ethoxylated tertiary amine of the formula RlN(C~2CH2-OH)2 wherein Rl is a C8 18 aliphatic hydrocarbon radical, the weight ratio of components (B)(l) to (B)(2) be1ng within the range of about 4.0:1.0 to 6.0:1,0. A more preferred component S (B)(l) member is a free acid of a complex organic phosphate ester of aromatic or aliphatic hydrophobe base and a prefexred component (B)(2) member is an ethoxylated tertiary amine derived frGm oxx~t oil, ~an oil, cott~d oil, ~m oil or tallow, exRmplified by o~n~rcially-available surfactants such as Ethomeen*C/12, C/15, C~20, C/25, S/12, S/15, S/20, T/12, T/13, T/20, etc. Preferred emLlsifiable concentrates herQ~ are ~x~e wh~n CampOn~lt (A) is selected ~xm the qroup consisting of alachlor, but~or, acet~or, metolachlor, triallate, trifluralin, and but,vLate.
Preferred EC's according to this invention are described in Examples 1-8 below.
Example 1 In this example, a 4 lb/gal (0.48 kg/l) EC formulation of alachlor is described.
Ingredients Weight Percent Alachlor (91% assay) 49.63 GAFAC RE-610 4.125 Ethomeen*C/12 0.875 Mazu DF-lOOs* 0.010 Methyl violet 0.017 Solvent (monochloro-benzene and T-400) 45.343 100.00 Example 2 This example describes a 5 lb/gal (0.6 kg/1) EC
formulation of butachlor.
In~redients Weight Percent ~utachlor (89~ assay~ 65.46 GAFAC RM 510 4,125 Ethomeen*C/12 0.375 Methyl violet Q.017 Mazu DF-lOOs* 0.01 T500-100 29.~13 100 . 00 * Trademarks . _ . ,, . _ _ ~ 1 1 7~85~ AG-1214 Example 3 This ex~mple describes a 4 lb/gal EC formulation of acetochlor.
Ingredients Weight Percent Acetochlor (93% assay) - 51.59 GAFAC RE-610 8.25 Ethomeen C/12 1.75 T-500-100 38.41 i00 . 00 Example 4 This example describes a 4 lb/gal EC formulatiorL of metolachlor.
Inqredients Weight Percent Metolachlor (93.77%) 48.19 GAFAC RE-610 2.00 GAFAC PE-510 2.00 Ethomeen C/12 1.00 Solvent (T400 and monochlorobenzene) 46.81 Example 5 A 4 lb/gal EC formulation of triallate is described in this example.
Ingredients Weight Percent Triallate (91~) 43.27 GAFAC RE-610 1.80 GAFAC 2E-510 2.70 Ethomeen C/12 0.50 Xylene 51.73 100 . 00 Example 6 This example describes a 7 lb/gal (0.84 kg/l) EC
formulation o~ butylate, ~ ~7~8~
IngredientsWeight Percent Butylate (100%)90 00 GAFAC RE-610 3.60 GAFAC PE-510 5.40 Ethomeen* C/121.00 100 . 00 Example 7 This example describes a 7 lb/gal EC of butylate containing as an antidote the compound N,N-diallyl-2,2-dichloroacetamide.
IngredientsWeight Percent Butylate (100%)85.83 Antidote 4.17 GAFAC RE-610 3.60 Ethomeen* C/121.00 100 . 00 Example 8 This example illustrates a 4 lb/gal EC formula-tion of trifluralin.
IngredientsWeight Percent Trifluralin (95%)48.32 Flo MO6NP* 4.25 Ethomeen* C/120.75 Solvent (T 400)46.68 100 . 00 In order to demonstrate the compatibility and stability of the EC's of this invention in emulsions of water and fluid fertilizers, a series of tests were run using a variety of emulsification systems according to this invention. In these tests, the water used conformed to World Health Organization (WHO) standard water, defined as a combination hard water of 342 ppm hardness (0.304 g.
CaC12, anhydrous or 0.4027 g. cacl2.2H2o~ plus 0.139 g. MgC12.6H2O plus distilled water to make 1 liter). The fertilizer solution used was a 28% nitrogen * Trademarks 8~
solution fer~ilizer made up by dissolving 496.4 g. of NH4NO3 and 396.8 g. of urea in 386.56 g. distilled water to make a one liter solution.
In conducting the stability tests in the fluid fertilizer solution approximately 1.6 ml of the EC is added to 40 mls of fertilizer solution in a suitable container which is then stoppered and vigorously shaken. Volume percent separation of oil is observed and determined after 15 minutes.
In conducting the water tests, both for spontaniety ("bloom") and stability, a measured volume of the EC is poured into the water in a suitable container, e.g., a Nessler tube, via a funnel and observing the degree of spontaneous emulsifi-cation. After the emulsion cloud reaches the bottom of the tube, the tube is stoppered, inverted 15 times and observed after 15 minutes and/or one hour for any separation. This test is usually run at a dilution rate of 1:19, e.g., 5 ml of EC in 95 ml water. The criteria for judging spontaniety is as follows: "Perfect" - a thick emulsion clou~ descending to the bottom of the tube without separation of any type; "Good" -thin "bloom" or cloud with no separation or thick cloud withminor separation such as emulsion trails at 1" (2.5 cm) or less from the bottom of the tube, "flc,wering", etc., and "Poor" -emulsion cloud containing oil droplets with oil separation from cloud above 1" from bottom of the tube. The criteria for measuring stability is the formation of 2 ml or less cream and no oil in WHO water and 5 ml or less cream and no oil in soft and hard waters; "soft water" is defined as having 114 ppm hardness prepared by diluting 1 part WHO hard water (defined above) with 2 parts of distilled water, and "hard water" is defined as 1000 ppm all calciu~ (prepared by dissolving 1.4691 g. of 100% CaC12~2~2O in distilled water and diluting to 1 liter) = 1000 ppm CaCO3 The volume separation in mls is converted by formula into volume percent separation.
In ~able 1 data is presented for tests at 25C of a plurality of emulsification systems for alachlor as the active I J ~85~
ingredient (component (A~) in the above EC description. In these tests, the phosphate ester component ((B)(l) above) was a mixture of mono- and di-phosphate esters of ethoxylated nonylphenol and the amine component ((B)(l)(a)-(f)) in the S above EC description is identified as in Examples 9-20. All the surfactants used herein, both phosphate esters and amines are available from commercial surfactant suppliers.
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As will be apparent from the stability data in Table 1, the EC's according to this invention were all perfectly stable 15 minutes after emulsification. The significance of this stability data will be more appreciated by reference to the stability data for commercial EC's set forth in Table 2 below according to test procedures described above.
In Table 2, under the first column are listed various EC's; these EC's were tested i.n waters of various hardness ranging from soft through WHO to hard waters indicated under the second column and in liquid fertilizer solutions of 28%
nitrogen ("LF" in second column~. The properties of the tested EC's are shown under the columns entitled "Spontaneity" for water and "Stabil.ity" in water and liquid fertilizer; the data for the invention EC's is listed side-by-side that for EC's now in commercial use. ~s stated earlier herein, since EC
formulations of a particular composition which are stable in water are unstable in liquid fertilizers and vice-versa, the result is a necessity to resort to two distinct EC's dif-ferently formulated in order to obtain maximum stability in the different emulsion bases. Thus, in Table 2, Formulation A is a commercial "water-grade" EC containing alachlor as the active ingredient and Eormulation B is a differently-formulated commercial alachlor EC for use in liquid fertilizers.
Similarly, Formulation C is a water-grade butachlor EC and Formulati.on D is a fertilizer-grade butachlor EC. The emulsification systems of the commercial EC's are proprietary to the manufacturers, but are of no significance for purposes of these tests other than to show the overall inferiority thereof relative to the unique emulsification system of this invention.
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,¢ E3 ~ h ~1 ~ ~ 70~356 Analysis of the data in Table 2 immediately points up the overall outstanding superiority of the invention EC'S both on an absolute basis and as compared to typical EC/s of leading commercial herbicides. In more particular, it will be noted that the invention EC's: (1) generally rate "Perfect" in spon-taneity in all waters; (2) maintain 100~ stability (i.e., zero % separation) after 15 minutes with all active ingredients tested in both waters and liquid fertilizers and (3) as a corollary to (2), utilizes a single emulsification system for both waters of all hardnesses and for liquid fertilizers. In contrast, the prior art commercial EC's are shown to exhibit such deficiencies as: (1) lack of either uniform spontaneity in water and/or stability in both water and fluid fertilizers;
while generally exhibiting good stability in water, the commer-cial EC' 5 are uniformly unstable in liquid fertilizers, except as in the case of Formulations B and D where two (2~ distinct formulations are required to obtain a modicum of stability and (3) when resort is had to different ~ormulations, spon-taneity and/or stability suffers with respect to the other base, whether water or liquid fertilizer. That is, e.g., while spontaneity of water-grade Formul~ations A and C is "Perfect" in water, their stability exhibits from 50-60% separ-ation in liquid fertilizers. Even more pronounced, the stability of fertilizer grade EC's B and D exhibit up to 60~ separation in liquid ferti]izer, and their spontaneity is "Poor" in all waters. Concomitantly, when changing formulations to accommo-date different base systems, it is commonly required to add nonionic and anionic surfactants to balance the hydrophilic and lipophilic properties of the system ("HLB"). The present invention eliminates any need for consideration ~ 3 708~6 and cost of additional surfactants to achieve any required .HLB criteria.
In additional comparati~e tests, the EC of Example 1 was tested with and without added stabilizer; it is known that EC B in Table 2 requires and contains an added stabilizer.
These test results showed that zero separation (100% stability) occurred after 15 minutes at 60C according to standard test methods. It is thus shown that the unique emulsification system of this invention has the important added advantage of eliminating the necessity to use and cost of added stabilizers in commercial EC's.
An even more profound demonstration of the outstand-ing advantages of the EC's of this invention is shown in long-term stability tests. The EC's of Examples 1-3 were further tested according to the above test protocol in WHO water and 28% liquid fertilizer solution; samples of the EC of Example 1 included material both with and without added stabilizer.
The data from these tests showed that there was zero percent phase separation and no decomposition or deterioration of active ingredient even after aging for a month at 60C.
The benefits of long-terils~ability in such ~n~sions is manifest, e.g., with respect to shelf-life, warehousing, transporting and use of product. These stability data are to be contrasted with prior art and curren~ commercial liquid ~ertili~er e~ulsions 2~ which are physically stable in t~ of only a few hcurs.
An incidental, but important~ additional advantage accruing from the discovery of the ECIs herein is the elimina-tion of analytical test procedures desi~ed to determine tlle ~ ~ 708~
..
"redispersability" properties of em~lsionsr.~e from kno~l and eKp~cm ntal æ~S. Due to the instability of such emLlsions, phase - - - separa~on occurs when ~le C is diluted in mLK tanks .. . ..
and allowed to sit. The formulation must then be agitated, stirred or shaken to redisperse the ingredients. Hence, analytical tests have been developed to determine the re-dispersability property of the emulsions. The EC's of the present invention render such redispersion tests obsolete; by itself a marked advance in the art.
Yet another important contribution to the EC art, the present EC's provide markedly enhanced corrosion inhi-bition vis-a-vis other known fertilizer grade formulations of the prior art, both "dry" and in the presence o water. As an illustration of the increased corrosion inhibition, the EC of Example 1 was compared with the commercial fertilizer-grade EC of Formulation B in Table 2; both of these EC's contain alachlor as the active ingredient. The comparative data is shown in Tables 3 and 4. In Table 3 is summarized the corrosion rates of the compared EC's on mild steel, in the dry state and containing various amounts of added water;
data based on accelerated static corrosion tests for 3 days at 50C. In Table 4 is summarized the corrosion rates of steel, aluminum and zinc, again with and without added water.
Test conditions were static partial i.mmersion for 3 days at 49C.
TA~LE 3 Corrosion in Mils Per Year Water Added (%) Formulation ~y~0.5 1.0 2.0 -B 2.010.0 46.4 52.9 Example 1 Nil4.0 29.2 38.1 Analysis of the data in Tahle 3 shows that the EC of Example 1 is unexpectedly superior to EC B from the stand-point of corrosion inhibition. In terms of percentages the EC of Example 1 is 200%, 60%, 37~ and 28~, respectively, less corrosive than EC B in the dry state and with 0.5~, 1.0% and 2.0%, respectively, water added.
-23- ~ 7~ AG-1214 ~ABLE 4 Corrosion Rate in Mils Per Year Formulation SteelAluminum Zinc B - "Dry" 2.0 0.4 180.0 Ex. 1 - "Dry" Nil Nil 7.7 B - 2% H2O 52.9 14.2 245.0 Ex. 1 - 2% H2O 38.1 Nil 6.6 Analysis of the data in Table 4 shows that the anti-corrosion properties of the EC of Example 1 is significantly superior to those of EC B with respect to the three metals tested. In particular, it is noted that the EC of Example 1 is non-corrosive in the dry state in steel and aluminum and in aluminum even when containing 2% water. An out-standing improvement in corrosion resistance in zinc is shown by the EC of Example 1 vis-a-vis that of EC B in both dry and wet states; notable imProvement i5 also shown in the EC
of 2~ample 1 cver EC ~ when each contains 2~ water in aluminum.
.. . . .. .
.
The particular significance for comparative tests of the respective EC's in steel, aluminum and zinc is that these are the primary metals used in the containers ~hen the EC's are transported, shelved, warehoused and/or mixed by formulators, distributors and farmers.
Emulsifiable concentrates according to this invention have been widely tested as herbicides in the field in numerous crops and weeds. It has been found that there are no significant differences in crop safety or yield or in weed control between the EC's of this invention and analo-gous ones of the prior art not containing the unique emulsi-fication system of this invention. Typical of such fieldtests are illustrated in Examples 21-36 in Tables 5-7. The data in these tables represents a composite summary of ~~~3~ tests conducted in many different states across America.
These tests involved applying herbicidal formulations of 1 1 70B~ 6 Formulations A and B (Table 2) and Example 1 to corn, soybeans and snapbeans under identical conditions. tn Tables 5-7 are shown in the columns from left to right, the example number, particular formulation, carrier volume in gallons/acre (liters/hectare), application rate of active ingredient (alachlor) in pounds/acre (kg/hectare), appli-cation mode, i.e., whether pre-emergence ("Pre") or pre-plant incorporated ("PPI"); "DAT" represents the number of days after treatment of the plants that observations were made and recorded, the crop and weeds (a dash "-" indicates species not in test) and the percent injury to the plants in terms of stand reduction and the states in which the tests were conducted. The letter symbols "a....l" represent weeds according to the following legend:
a - Yellow nutsedge g - Barnyard grass b - Lambsquarter h - Common purslane c - Green foxtail i - Seedling Johnsongrass d - Velvetleaf j - Pennsylvania Smartweed e - Giant foxtail k - Redroot pigweed f - Large crabgrass 1 - ~ellow foxtail ~ ~ 7~6 ~3 H ~ H 1 O O
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Analysis of the data in Tables 5-7 leads to a con-clusion that the herbicidal alachlor EC of Example 1, representative of this invention, and the current water-grade alachlor formulation (EC A) and fertilizer-grade alachlor formulation (EC B) perform essentially identically under comparable test conditions and locations, with an exception or two which under replication would undoubtedly level out.
It will,therefore, be manifestly apparent that the broad spectrum performance of the EC's of this invention is unique in this field. Thus, in summary, the outstanding advantages and improvements of the EC's of the present invention over prior art EC's are as follows:
1. A single, homogeneous EC which is compatible with and physically stable in both water (of all normal degrees of hardness, including WHO) and in fluid fertilizers.
2. Long-term stability; some EC's of the invention have survived aging for at least one month.
3. Corrosion inhibition improvement shown by orders of magnitude in some cases.
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,¢ E3 ~ h ~1 ~ ~ 70~356 Analysis of the data in Table 2 immediately points up the overall outstanding superiority of the invention EC'S both on an absolute basis and as compared to typical EC/s of leading commercial herbicides. In more particular, it will be noted that the invention EC's: (1) generally rate "Perfect" in spon-taneity in all waters; (2) maintain 100~ stability (i.e., zero % separation) after 15 minutes with all active ingredients tested in both waters and liquid fertilizers and (3) as a corollary to (2), utilizes a single emulsification system for both waters of all hardnesses and for liquid fertilizers. In contrast, the prior art commercial EC's are shown to exhibit such deficiencies as: (1) lack of either uniform spontaneity in water and/or stability in both water and fluid fertilizers;
while generally exhibiting good stability in water, the commer-cial EC' 5 are uniformly unstable in liquid fertilizers, except as in the case of Formulations B and D where two (2~ distinct formulations are required to obtain a modicum of stability and (3) when resort is had to different ~ormulations, spon-taneity and/or stability suffers with respect to the other base, whether water or liquid fertilizer. That is, e.g., while spontaneity of water-grade Formul~ations A and C is "Perfect" in water, their stability exhibits from 50-60% separ-ation in liquid fertilizers. Even more pronounced, the stability of fertilizer grade EC's B and D exhibit up to 60~ separation in liquid ferti]izer, and their spontaneity is "Poor" in all waters. Concomitantly, when changing formulations to accommo-date different base systems, it is commonly required to add nonionic and anionic surfactants to balance the hydrophilic and lipophilic properties of the system ("HLB"). The present invention eliminates any need for consideration ~ 3 708~6 and cost of additional surfactants to achieve any required .HLB criteria.
In additional comparati~e tests, the EC of Example 1 was tested with and without added stabilizer; it is known that EC B in Table 2 requires and contains an added stabilizer.
These test results showed that zero separation (100% stability) occurred after 15 minutes at 60C according to standard test methods. It is thus shown that the unique emulsification system of this invention has the important added advantage of eliminating the necessity to use and cost of added stabilizers in commercial EC's.
An even more profound demonstration of the outstand-ing advantages of the EC's of this invention is shown in long-term stability tests. The EC's of Examples 1-3 were further tested according to the above test protocol in WHO water and 28% liquid fertilizer solution; samples of the EC of Example 1 included material both with and without added stabilizer.
The data from these tests showed that there was zero percent phase separation and no decomposition or deterioration of active ingredient even after aging for a month at 60C.
The benefits of long-terils~ability in such ~n~sions is manifest, e.g., with respect to shelf-life, warehousing, transporting and use of product. These stability data are to be contrasted with prior art and curren~ commercial liquid ~ertili~er e~ulsions 2~ which are physically stable in t~ of only a few hcurs.
An incidental, but important~ additional advantage accruing from the discovery of the ECIs herein is the elimina-tion of analytical test procedures desi~ed to determine tlle ~ ~ 708~
..
"redispersability" properties of em~lsionsr.~e from kno~l and eKp~cm ntal æ~S. Due to the instability of such emLlsions, phase - - - separa~on occurs when ~le C is diluted in mLK tanks .. . ..
and allowed to sit. The formulation must then be agitated, stirred or shaken to redisperse the ingredients. Hence, analytical tests have been developed to determine the re-dispersability property of the emulsions. The EC's of the present invention render such redispersion tests obsolete; by itself a marked advance in the art.
Yet another important contribution to the EC art, the present EC's provide markedly enhanced corrosion inhi-bition vis-a-vis other known fertilizer grade formulations of the prior art, both "dry" and in the presence o water. As an illustration of the increased corrosion inhibition, the EC of Example 1 was compared with the commercial fertilizer-grade EC of Formulation B in Table 2; both of these EC's contain alachlor as the active ingredient. The comparative data is shown in Tables 3 and 4. In Table 3 is summarized the corrosion rates of the compared EC's on mild steel, in the dry state and containing various amounts of added water;
data based on accelerated static corrosion tests for 3 days at 50C. In Table 4 is summarized the corrosion rates of steel, aluminum and zinc, again with and without added water.
Test conditions were static partial i.mmersion for 3 days at 49C.
TA~LE 3 Corrosion in Mils Per Year Water Added (%) Formulation ~y~0.5 1.0 2.0 -B 2.010.0 46.4 52.9 Example 1 Nil4.0 29.2 38.1 Analysis of the data in Tahle 3 shows that the EC of Example 1 is unexpectedly superior to EC B from the stand-point of corrosion inhibition. In terms of percentages the EC of Example 1 is 200%, 60%, 37~ and 28~, respectively, less corrosive than EC B in the dry state and with 0.5~, 1.0% and 2.0%, respectively, water added.
-23- ~ 7~ AG-1214 ~ABLE 4 Corrosion Rate in Mils Per Year Formulation SteelAluminum Zinc B - "Dry" 2.0 0.4 180.0 Ex. 1 - "Dry" Nil Nil 7.7 B - 2% H2O 52.9 14.2 245.0 Ex. 1 - 2% H2O 38.1 Nil 6.6 Analysis of the data in Table 4 shows that the anti-corrosion properties of the EC of Example 1 is significantly superior to those of EC B with respect to the three metals tested. In particular, it is noted that the EC of Example 1 is non-corrosive in the dry state in steel and aluminum and in aluminum even when containing 2% water. An out-standing improvement in corrosion resistance in zinc is shown by the EC of Example 1 vis-a-vis that of EC B in both dry and wet states; notable imProvement i5 also shown in the EC
of 2~ample 1 cver EC ~ when each contains 2~ water in aluminum.
.. . . .. .
.
The particular significance for comparative tests of the respective EC's in steel, aluminum and zinc is that these are the primary metals used in the containers ~hen the EC's are transported, shelved, warehoused and/or mixed by formulators, distributors and farmers.
Emulsifiable concentrates according to this invention have been widely tested as herbicides in the field in numerous crops and weeds. It has been found that there are no significant differences in crop safety or yield or in weed control between the EC's of this invention and analo-gous ones of the prior art not containing the unique emulsi-fication system of this invention. Typical of such fieldtests are illustrated in Examples 21-36 in Tables 5-7. The data in these tables represents a composite summary of ~~~3~ tests conducted in many different states across America.
These tests involved applying herbicidal formulations of 1 1 70B~ 6 Formulations A and B (Table 2) and Example 1 to corn, soybeans and snapbeans under identical conditions. tn Tables 5-7 are shown in the columns from left to right, the example number, particular formulation, carrier volume in gallons/acre (liters/hectare), application rate of active ingredient (alachlor) in pounds/acre (kg/hectare), appli-cation mode, i.e., whether pre-emergence ("Pre") or pre-plant incorporated ("PPI"); "DAT" represents the number of days after treatment of the plants that observations were made and recorded, the crop and weeds (a dash "-" indicates species not in test) and the percent injury to the plants in terms of stand reduction and the states in which the tests were conducted. The letter symbols "a....l" represent weeds according to the following legend:
a - Yellow nutsedge g - Barnyard grass b - Lambsquarter h - Common purslane c - Green foxtail i - Seedling Johnsongrass d - Velvetleaf j - Pennsylvania Smartweed e - Giant foxtail k - Redroot pigweed f - Large crabgrass 1 - ~ellow foxtail ~ ~ 7~6 ~3 H ~ H 1 O O
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Analysis of the data in Tables 5-7 leads to a con-clusion that the herbicidal alachlor EC of Example 1, representative of this invention, and the current water-grade alachlor formulation (EC A) and fertilizer-grade alachlor formulation (EC B) perform essentially identically under comparable test conditions and locations, with an exception or two which under replication would undoubtedly level out.
It will,therefore, be manifestly apparent that the broad spectrum performance of the EC's of this invention is unique in this field. Thus, in summary, the outstanding advantages and improvements of the EC's of the present invention over prior art EC's are as follows:
1. A single, homogeneous EC which is compatible with and physically stable in both water (of all normal degrees of hardness, including WHO) and in fluid fertilizers.
2. Long-term stability; some EC's of the invention have survived aging for at least one month.
3. Corrosion inhibition improvement shown by orders of magnitude in some cases.
4. Elimination of the following (a) Added stabilizers;
(b) Anionic and nonionic surfactants previously required for ~Ibutting~
and HLB balancing, and (c) Analytical test procedures for redispersability.
(b) Anionic and nonionic surfactants previously required for ~Ibutting~
and HLB balancing, and (c) Analytical test procedures for redispersability.
5. A unitary container; it is no longer necessary to provide separate containers of different matexials having differing anti-corrosion properties for water-grade and fertilizer-grade EC's and
6. The improved EC's of this invention exhibit the same herbicidal properties as prior art herbicides having the same active ingredient with respect to crop safe~y and weed control.
The general parameters of the EC's and dispersions _30_ ~1 7~56 AG-1214 thereof have been outlined above. However, it may be pointed out that in the experience of the assignee herein, the preferred active ingredients herein are 2-haloacetani-lides wherein the 5~-halogen is chlorine or bromine; the anilide ring is substituted with hydrogen, Cl 6 alkyl, alkoxy or alkoxyalkyl radicals, preferably one or both ortho positions relative to the anilide nitrogen being occu-pied with alkyl and/or alkoxy radicals and, occasionally a further addition of one or two alkyl and/or alkoxy ring substitutions notably in the meta positions. The preferred R members are hydrogen, Cl 4 alkyl radicals or an alkoxy-alkyl radical having up to 12 carbon atoms, up to 8 of which may be in the alkoxy moiety and up to 4 of which may be in the alkyl moiety.
Representative straight or branched alkyls (the term embraces primary, secondary and tertiary alkyls) include methyl, ethyl, propyl, the butyls, pentyls, hexyls, heptyls, octyls, nonyls, decyls, undecyls and dodecyls.
Representative alkenyl members include vinyl, allyl, crotyl, methallyl and ethylenically unsaturated analogs of the above alkyls.
Representative alkynyls include ethynyl, the propynyls, butynyls and acetylenically unsaturated analogs of the above alkyls.
Representative alkoxy radicals include methoxy, ethoxy, propoxy, butoxy, etc., and the isomeric alkoxys thereof.
Representative alkoxyalkyls include methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, isobutoxymethyl, tert-butoxymethyl, the isomeric amyloxy-methyls, hexyloxymethyls, etc., and the corresponding alkoxyethyls, alkoxypropyls and alkoxybutyls, all of which may be substituted with non-interfering groups, e.g., lower alkyl, etc., aliphatic m~mbers of which contain up to 4 carbons.
Representative heterocycles and heterocyclylalkyls include furanyl, furfuryl, tetrahydrofuryl, tetrahydro-furfuryl, pyxanyl, tetrahydropyranyl, thienyl, pyrrolyl, pyrazolyl, thiazole, oxazinyl, triazinyl, etc.
Representative cycloalkyl and cycloalkylalkyl radicals include cyclopropyl, cyclo~utyl, cyclopentyl, cyclohexyl, -31- ~1 70 ~ 5 ~ AG-1214 cycloheptyl, cyclopropylmethyl, cyclobutylmethyl, etc.
Representative aryl, aralkyl and alkaryl radicals include phenyl, benzyl, tolyl, xylyl, naphthyl, methyl-phenyl, ethylphenyl, etc.
While the various components of the EC's herein have been generally disclosed and particularly descrlbed in specific working embodiments, it will be apparent to those skilled in the art ~hat modificAtions and variations can be made without departlng from the spirit and scope of this invention. Illustrative of such modifications are the combination of one or more biologically-active ingredients that complement one another, e.g., the combination of different herbicides that effectively control different weeds such as alachlor plu5 atrazine, linuron, metribuzin, etc. Also, it is within the purview of this invention to combine various phosphate esters and/or amines of the present emulsification system to achieve the same or modified emulsification effects. In like manner, various solvents may be mixed to effect cost or performance optima.
The fluid fertillzers herein include water-soluble or suspensions of nitrogen, potassium ant~/or phosphate salts railging from 3-18-1~ and a 10-34-0 analysis to 32% nitroqe solution, e.g., derived from urea and ammonium nitrate.
The foregoing description is understood to be exemplary and not exhaustive of the scope of the invention which otherwise is defined by the claims herein.
The general parameters of the EC's and dispersions _30_ ~1 7~56 AG-1214 thereof have been outlined above. However, it may be pointed out that in the experience of the assignee herein, the preferred active ingredients herein are 2-haloacetani-lides wherein the 5~-halogen is chlorine or bromine; the anilide ring is substituted with hydrogen, Cl 6 alkyl, alkoxy or alkoxyalkyl radicals, preferably one or both ortho positions relative to the anilide nitrogen being occu-pied with alkyl and/or alkoxy radicals and, occasionally a further addition of one or two alkyl and/or alkoxy ring substitutions notably in the meta positions. The preferred R members are hydrogen, Cl 4 alkyl radicals or an alkoxy-alkyl radical having up to 12 carbon atoms, up to 8 of which may be in the alkoxy moiety and up to 4 of which may be in the alkyl moiety.
Representative straight or branched alkyls (the term embraces primary, secondary and tertiary alkyls) include methyl, ethyl, propyl, the butyls, pentyls, hexyls, heptyls, octyls, nonyls, decyls, undecyls and dodecyls.
Representative alkenyl members include vinyl, allyl, crotyl, methallyl and ethylenically unsaturated analogs of the above alkyls.
Representative alkynyls include ethynyl, the propynyls, butynyls and acetylenically unsaturated analogs of the above alkyls.
Representative alkoxy radicals include methoxy, ethoxy, propoxy, butoxy, etc., and the isomeric alkoxys thereof.
Representative alkoxyalkyls include methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, isobutoxymethyl, tert-butoxymethyl, the isomeric amyloxy-methyls, hexyloxymethyls, etc., and the corresponding alkoxyethyls, alkoxypropyls and alkoxybutyls, all of which may be substituted with non-interfering groups, e.g., lower alkyl, etc., aliphatic m~mbers of which contain up to 4 carbons.
Representative heterocycles and heterocyclylalkyls include furanyl, furfuryl, tetrahydrofuryl, tetrahydro-furfuryl, pyxanyl, tetrahydropyranyl, thienyl, pyrrolyl, pyrazolyl, thiazole, oxazinyl, triazinyl, etc.
Representative cycloalkyl and cycloalkylalkyl radicals include cyclopropyl, cyclo~utyl, cyclopentyl, cyclohexyl, -31- ~1 70 ~ 5 ~ AG-1214 cycloheptyl, cyclopropylmethyl, cyclobutylmethyl, etc.
Representative aryl, aralkyl and alkaryl radicals include phenyl, benzyl, tolyl, xylyl, naphthyl, methyl-phenyl, ethylphenyl, etc.
While the various components of the EC's herein have been generally disclosed and particularly descrlbed in specific working embodiments, it will be apparent to those skilled in the art ~hat modificAtions and variations can be made without departlng from the spirit and scope of this invention. Illustrative of such modifications are the combination of one or more biologically-active ingredients that complement one another, e.g., the combination of different herbicides that effectively control different weeds such as alachlor plu5 atrazine, linuron, metribuzin, etc. Also, it is within the purview of this invention to combine various phosphate esters and/or amines of the present emulsification system to achieve the same or modified emulsification effects. In like manner, various solvents may be mixed to effect cost or performance optima.
The fluid fertillzers herein include water-soluble or suspensions of nitrogen, potassium ant~/or phosphate salts railging from 3-18-1~ and a 10-34-0 analysis to 32% nitroqe solution, e.g., derived from urea and ammonium nitrate.
The foregoing description is understood to be exemplary and not exhaustive of the scope of the invention which otherwise is defined by the claims herein.
Claims (74)
1. An emulsifier composition comprising, in combination:
(1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8-20 aliphatic alcohols, and (2) one or more amines selected from the group consisting of:
(a) fatty tertiary amines of the formula R1N(R)2;
(b) fatty amine oxides of the formula R1?(CH2CH2OH)2;
(c) beta-amines of the formula H3CCH(NH2)R1;
(d) amido-bridged tertiary amines of the formula R1CON(CH2)3N(R)2;
(e) ethoxylated tertiary amines of the formulae:
(i) R1N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1(CH2)3N(CH2CH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines;
where R is a C1-5 alkyl radical and R1 is a C8-18 aliphatic hydrocarbon radical; and wherein the weight ratio of components (1) to (2) is within the range of about 1:1 to about 10:1.
(1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8-20 aliphatic alcohols, and (2) one or more amines selected from the group consisting of:
(a) fatty tertiary amines of the formula R1N(R)2;
(b) fatty amine oxides of the formula R1?(CH2CH2OH)2;
(c) beta-amines of the formula H3CCH(NH2)R1;
(d) amido-bridged tertiary amines of the formula R1CON(CH2)3N(R)2;
(e) ethoxylated tertiary amines of the formulae:
(i) R1N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1(CH2)3N(CH2CH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines;
where R is a C1-5 alkyl radical and R1 is a C8-18 aliphatic hydrocarbon radical; and wherein the weight ratio of components (1) to (2) is within the range of about 1:1 to about 10:1.
2. The emulsifier composition of claim 1 wherein component (2) is an ethoxylated tertiary amine of the formula R1N(CH2CH2OH)2 wherein R1 is a C8-18 aliphatic hydrocarbon radical, the weight ratio of components (1) to (2) being within the range of about 4.0:1.0 to 6.0:1Ø
3. The emulsifier composition of claim 2 wherein component (1) is a mixture of mono- and diphosphate esters of ethoxylated nonylphenol.
4. The emulsifier composition according to claim 3 wherein component (1) is a free acid of a complex organic phosphate ester of aromatic or aliphatic hydrophobe base and component (2) is as defined in claim 3 having 12 carbon atoms.
5. An emulsifiable concentrate comprising:
(A) at least one biologically-active compound selected from the group consisting of substituted acetanilides thiocarbamates and anilines;
(B) an emulsifier system comprising:
(1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8-20 aliphatic alcohols, and (2) one or more amines selected from the group consisting of:
(a) fatty tertiary amines of the formula R1N(R)2;
(b) fatty amine oxides of the formula R1?(CH2CH2OH)2;
(c) beta-amines of the formula H3CCH(NH2)R1:
(d) amido-bridged tertiary amines of the formula R1CON(CH2)3N(R)2;
(e) ethoxylated tertiary amines of the formulae:
(i) R1N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1(CH2)3N(CH2CH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines;
where R is a C1-5 alkyl radical and R1 is a C8-18 aliphatic hydrocarbon radical, and wherein the weight ratio of components (B)(1) to (B)(2) is in the range of about 1:1 to about 10:1.
(A) at least one biologically-active compound selected from the group consisting of substituted acetanilides thiocarbamates and anilines;
(B) an emulsifier system comprising:
(1) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8-20 aliphatic alcohols, and (2) one or more amines selected from the group consisting of:
(a) fatty tertiary amines of the formula R1N(R)2;
(b) fatty amine oxides of the formula R1?(CH2CH2OH)2;
(c) beta-amines of the formula H3CCH(NH2)R1:
(d) amido-bridged tertiary amines of the formula R1CON(CH2)3N(R)2;
(e) ethoxylated tertiary amines of the formulae:
(i) R1N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1(CH2)3N(CH2CH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines;
where R is a C1-5 alkyl radical and R1 is a C8-18 aliphatic hydrocarbon radical, and wherein the weight ratio of components (B)(1) to (B)(2) is in the range of about 1:1 to about 10:1.
6. An emulsifiable concentrate according to claim 5 further including a solvent.
7. Emulsifiable concentrate according to claim 5 wherein component (A) is present in a herbicidally effective amount within the range of about 5.0 - 98.0% by weight, component (B) is present in an amount within the range of about 2.0 - 50.0%
by weight and the balance is a solvent.
by weight and the balance is a solvent.
8. Emulsifiable concentrate according to claim 5 wherein component (B)(1) is a mixture of mono- and diphosphate esters of ethoxylated nonylphenol and component (B)(2) is an ethoxylated tertiary amine of the formula R1N(CH2CH2OH)2 wherein R1 is a C8-18 aliphatic hydrocarbon radical, the weight ratio of com-ponents (B)(1) to (B)(2) being within the range of about 4.0:1.0 to 6.0:1Ø
9. Emulsifiable concentrate according to claim 8 wherein component (B)(1) is a free acid of a complex organic phosphate ester of aromatic or aliphatic hydrophobe base and component (B)(2) is as defined in claim 8 having 12 carbon atoms.
10. Emulsifiable concentrate according to claim 5 wherein component (A) is present in a herbicidally effective amount within the range of about 5.0 - 98.0% by weight, component (B) is present in an amount within the range of about 3.0 - 15.0%
by weight and the balance is a solvent.
by weight and the balance is a solvent.
11. Emulsifiable concentrate according to claim 9 wherein component (A) is a 2-haloacetanilide having the formula wherein X is chlorine, bromine or iodine;
n is an integer from 0-5 inclusive; and R2 and R3 represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxyalkyl or polyalkoxyalkyl groups having up to 18 carbon atoms, cycloalkyl, cycloalkyloxy or cycloalkylalkyl groups having up to 10 carbon atoms, aralkyl or alkaryl groups having up to 18 carbon atoms or O, S or N heterocyclyl or heterocyclylalkyl radicals having up to 7 ring members, and up to 3 carbons in the alkyl moiety, or said R2 and R3 members substituted with alkyl, alkenyl, alkynyl, halo, nitro, cyano, hydroxy, CF3, amino, mono- and dialkyl amino groups.
n is an integer from 0-5 inclusive; and R2 and R3 represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxyalkyl or polyalkoxyalkyl groups having up to 18 carbon atoms, cycloalkyl, cycloalkyloxy or cycloalkylalkyl groups having up to 10 carbon atoms, aralkyl or alkaryl groups having up to 18 carbon atoms or O, S or N heterocyclyl or heterocyclylalkyl radicals having up to 7 ring members, and up to 3 carbons in the alkyl moiety, or said R2 and R3 members substituted with alkyl, alkenyl, alkynyl, halo, nitro, cyano, hydroxy, CF3, amino, mono- and dialkyl amino groups.
12. Emulsifiable concentrate according to claim 11 wherein X is chlorine or bromine; n is an integer from 0-3 inclusive, R2 is hydrogen, C1-4 alkyl or a C1-12 alkoxyalkyl radical having up to 8 carbons in the alkoxy moiety and up to 4 carbons in the alkyl moiety and R3 is hydrogen or C1-8 alkyl, alkoxy or alkoxyalkyl radical.
13. Emulsifiable concentrate according to claim 12 wherein component (A) is 2',6'-diethyl-N-(methoxymethyl)-2-chloro-acetanilide ("alachlor").
14. Emulsifiable concentrate according to claim 12 wherein component (A) is 2',6'-diethyl-N-(butoxymethyl)-2-chloro-acetanilide ("butachlor").
15. Emulsifiable concentrate according to claim 12 wherein component (A) is 2'-ethyl-6'-methyl-N-(ethoxymethyl)-2-chloro-acetanilide ("acetochlor").
16. Emulsifiable concentrate according to claim 12 wherein component (A) is 2'-ethyl-6'-methyl-N-(1-methoxyprop-2-yl)-2-chloroacetanilide ("metolachlor").
17. Emulsifiable concentrate according to claim 12 wherein R2 is ethoxymethyl, n is 2, one R3 is 2'-trifluoromethyl and the other R3 is 6'-methyl or ethyl.
18. Emulsifiable concentrate according to claim 9 wherein component (A) is a thiocarbamate having the formula R4S?-N(R5)2 wherein R4 is a C1-4 alkyl or di- or trichloroallyl radical and R5 is a C1-4 alkyl radical.
19. Emulsifiable concentrate according to claim 18 wherein said thiocarbamate is S-2,3,3-trichloroallyl-diisopropylthio-carbamate ("triallate").
20. Emulsifiable concentrate according to claim 18 wherein said thiocarbamate is S-ethyl diisobutylthiocarbamate ("butylate").
21. Emulsifiable cbncentrate according to claim 18 wherein said thiocarbamate is S-ethyl di-n-propylthiocarbamate ("EPTC").
22. Emulsifiable concentrate according to claim 9 wherein component (A) is a compound having the formula wherein R6 is a C1-4 alkyl radical.
23. Emulsifiable concentrate according to claim 22 wherein said compound is 2,6-dinitro-4-trifluoromethylaniline ("trifluralin").
24. Emulsifiable-concentrate according to claim 11, 12 or 13 wherein a defoamer, odorant and/or dye is present.
25. Emulsifiable concentrate according to claim 14, 15 or 16 wherein a defoamer, odorant and/or dye is present.
26. Emulsifiable concentrate according to claim 17, 18 or 19 wherein a defoamer, odorant and/or dye is present.
27. Emulsifiable concentrate according to claim 20 or 21 wherein a defoamer, odorant and/or dye is present.
28. Emulsifiable concentrate according to claim 22 or 23, wherein a defoamer, odorant and/or dye is present.
29. Emulsifiable concentrate according to claim 11, 12 or 13 which further contains an antidote for component (A).
30. Emulsifiable concentrate according to claim 14, 15 or 16 which further contains an antidote for component (A).
31. Emulsifiable concentrate-according to claim 17, 18 or 19 which further contains an antidote for component (A;.
32. Emulsifiable concentrate according to claim 20 or 21 which further contains an antidote for component (A).
33. Emulsifiable concentrate according to claim 22 or 23 which further contains an antidote for component (A).
34. Emulsifiable concentrate according to claim 10 which further contains an antidote of ethyl 2-chloro-4-trifluoromethyl-5-thiazolecarboxylate or benzyl-2-chloro-4-trifluoromethyl-5-thiazolecarboxylate when component (A) is 2',6'-diethyl-N-(methoxymethyl)-2-chloroacetanilide; 2',6'-diethyl-N-(butoxymethyl)-2-chloroacetanilide; 2'-ethyl-6'-methyl-N-(ethoxymethyl)-2-chloroacetanilide; or 2'-ethyl-6'-methyl-N-(1-methoxyprop-2-yl)-2-chloroacetanilide.
35. Emulsifiable concentrate according to claim 10 which further contains an antidote of 3-(2',5'-dimethoxyphenacyl)-phthalide or ethyl 5-(2,4-dichlorophenyl)-4-isoxazolecarboxylate when component (A) is 2',6'-diethyl-N-(butoxymethyl)-2-chloroacetanilide.
36. Emulsifiable concentrate according to claim 10 which further contains an antidote of .alpha.-(cyanomethoxyamino)-benzaceto-nitrile when component (A) is 2'-ethyl-6'-methyl-N-(1-methoxy-prop-2-yl)-2-chloroacetanilide.
37. Emulsifiable concentrate according to claim 10 which further contains an antidote of N,N-diallyl-2,2-dichloroacetamide when component (A) is S-ethyl di-n-propylthiocarbamate or S-ethyl diisobutylthiocarbamate.
38. A physically stable emulsion comprising (I) water as the dispersion medium, or (II) a liquid fertilizer comprising solutions or suspensions of nitrogen, potassium and/or phosphate salts ranging from 3-18-18 and a 10-34-0 analysis to 32% nitrogen solution as the dispersion medium;
(III) at least one biologically-active compound selected from the group consisting of substituted 2-halo-acetanilides, carbamates and anilines and (IV) an emulsifier system comprising (A) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8-20 aliphatic alcohols and (B) one or more amines selected from the group consisting of:
(a) fatty tertiary amines of the formula R1N(R)2;
(b) fatty amine oxides of the formula R1?(CH2CH2OH)2;
(c) beta-amines of the formula H3CCH(NH2)R1;
(d) amido-bridged tertiary amines of the formula R1CON(CH2)3N(R)2;
(e) ethoxylated tertiary amines of the formulae:
(i) R1N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1(CH2)3N(CH2CH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines;
where R is a C1-5 alkyl radical and R1 is a C8-18 aliphatic hydrocarbon radical; and wherein the weight ratio of components (A) to (B) is within the range of about 1.0:1.0 to 10:1Ø
(III) at least one biologically-active compound selected from the group consisting of substituted 2-halo-acetanilides, carbamates and anilines and (IV) an emulsifier system comprising (A) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C8-20 aliphatic alcohols and (B) one or more amines selected from the group consisting of:
(a) fatty tertiary amines of the formula R1N(R)2;
(b) fatty amine oxides of the formula R1?(CH2CH2OH)2;
(c) beta-amines of the formula H3CCH(NH2)R1;
(d) amido-bridged tertiary amines of the formula R1CON(CH2)3N(R)2;
(e) ethoxylated tertiary amines of the formulae:
(i) R1N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1(CH2)3N(CH2CH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines;
where R is a C1-5 alkyl radical and R1 is a C8-18 aliphatic hydrocarbon radical; and wherein the weight ratio of components (A) to (B) is within the range of about 1.0:1.0 to 10:1Ø
39. An emulsifiable concentrate according to claim 38 further including a solvent.
40. Emulsion according to claim 38 wherein said dispersion medium is component (I) of soft, hard or WHO hardness.
41. Emulsion according to claim 38 wherein said dispersion medium is component (II).
42. Emulsion according to claim 41 wherein said liquid fertilizer is a nitrogen solution derived from urea and ammonium nitrate having up to 32% nitrogen.
43. Emulsion according to claim 40 wherein said emulsifier system comprises (a) a mixture of mono- and diphosphate esters of ethoxylated mono- and dinonyl phenols and (b) an ethoxylated tertiary amine of the formula R1N(CH2CH2OH)2 wherein R1 is an aliphatic hydrocarbon radical derived from coconut oil, castor oil or tallow.
44. Emulsion according to claim 41 wherein said emulsifier system comprises (a) a mixture of mono- and diphosphate esters of ethoxylated mono- and dinonyl phenols and (b) an ethoxylated tertiary amine of the formula R1N(CH2CH2OH)2 wherein R1 is an aliphatic hydrocarbon radical derived from coconut oil, castor oil or tallow.
45. Emulsion according to claim 40 wherein component (A) is a free acid of a complex organic phosphate ester of aromatic or aliphatic hydrophobe base and component (B) is a tertiary amine as defined in claim 43 having 12 carbon atoms, the weight ratio of (A) to (B) being within the range of about 4.0:1.0 to 6.0:1Ø
46. Emulsion according to claim 41 wherein component (A) is a free acid of a complex organic phosphate ester of aromatic or aliphatic hydrophobe base and component (B) is a tertiary amine as defined in claim 43 having 12 carbon atoms, the weight ratio of (A) to (B) being within the range of about 4.0:1.0 to 6.0:1Ø
47. Emulsion according to claim 38 wherein component (III) is a 2-haloacetanilide having the formula wherein X is chlorine, bromine or iodine;
n is an integer from 0-5 inclusive; and R2 and R3 represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxyalkyl or polyalkoxyalkyl groups having up to 18 carbon atoms, cycloalkyl, cycloalkyloxy or cycloalkylalkyl groups having up to 10 carbon atoms, aralkyl or alkaryl groups having up to 18 carbon atoms or O, S or N heterocyclyl or heterocyclylalkyl radicals having up to 7 ring members, and up to 3 carbons in the alkyl moiety, or said R2 and R3 members substituted with alkyl, alkenyl, alkynyl, halo, nitro, cyano, hydroxy, CF3, amino, mono- and dialkyl amino groups.
n is an integer from 0-5 inclusive; and R2 and R3 represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxyalkyl or polyalkoxyalkyl groups having up to 18 carbon atoms, cycloalkyl, cycloalkyloxy or cycloalkylalkyl groups having up to 10 carbon atoms, aralkyl or alkaryl groups having up to 18 carbon atoms or O, S or N heterocyclyl or heterocyclylalkyl radicals having up to 7 ring members, and up to 3 carbons in the alkyl moiety, or said R2 and R3 members substituted with alkyl, alkenyl, alkynyl, halo, nitro, cyano, hydroxy, CF3, amino, mono- and dialkyl amino groups.
48. Emulsion according to claim 47 wherein said dispersion medium is component (I) of soft, hard or WHO hardness.
49. Emulsion according to claim 47 wherein said dispersion medium is component (II).
50. Emulsion according to claim 47, 48 or 49 wherein X
is chlorine or bromine; n is an integer from 0-3 inclusive, R2 is hydrogen, C1-4 alkyl or a C1-12 alkoxyalkyl radical having up to 8 carbons in the alkoxy moiety and up to 4 carbons in the alkyl moiety and R3 is hydrogen or C1-8 alkyl, alkoxy or alkoxyalkyl radical.
is chlorine or bromine; n is an integer from 0-3 inclusive, R2 is hydrogen, C1-4 alkyl or a C1-12 alkoxyalkyl radical having up to 8 carbons in the alkoxy moiety and up to 4 carbons in the alkyl moiety and R3 is hydrogen or C1-8 alkyl, alkoxy or alkoxyalkyl radical.
51. Emulsion according to claim 47, 48 or 49 wherein component (III) is 2',6'-diethyl-N-(methoxymethyl)-2-chloro-acetanilide ("alachlor").
52. Emulsion according to claim 47, 48 or 49 wherein component (III) is 2',6'-diethyl-N-(butoxymethyl)-2-chloro-acetanilide ("butachlor").
53. Emulsion according to claim 47, 48 or 49 wherein component (III) is 2'-ethyl-6'-methyl-N-(ethoxymethyl)-2-chloro-acetanilide ("acetochlor").
54. Emulsion according to claim 47, 48 or 49 wherein component (III) is 2'-ethyl-6'-methyl-N-(1-methoxyprop-2-yl)-2-chloroacetanilide ("metolachlor").
55. Emulsion according to claim 47, 48 or 49 wherein in said herbicidal compound R2 is ethoxymethyl, n is 2, one R3 is 2'-trifluoromethyl and the other R3 is 6'-methyl or ethyl.
56. Emulsion according to claim 45 or 46 wherein component (III) is a thiocarbamate having the formula R4S? - N(R5)2 wherein R4 is a Cl 4 alkyl or di- or trichloroallyl radical and R5 is a C1-4 alkyl radical.
57. Emulsion according to claim 45 or 46 wherein component (III) is S-2,3,3-trichloroallyl-diisopropylthiocarbamate ("triallate").
58. Emulsion according to claim 45 or 46 wherein component (III) is S-ethyl diisobutylthiocarbamate ("butylate").
59. Emulsion according to claim 45 or 46 wherein component (III) is S-ethyl di-n-propylthiocarbamate ("EPTC").
60. Emulsion according to claim 45 or 46 wherein component (III) is a compound having the formula wherein R6 is a C1-4 alkyl radical.
61. Emulsion according to claim 45 or 46 wherein component (III) is 2,6-dinitro-4-trifluoromethylaniline ("trifluralin").
62. Emulsion according to claim 47, 48 or 49 wherein a defoamer, dye and/or odorant is present.
63. Emulsion according to claim 47, 48 or 49 which further contains an antidote for component (III).
64. Emulsion according to claim 47, 48 or 49 which further contains an antidote of ethyl 2-chloro-4-trifluoromethyl-5-thiazolecarboxylate or benzyl-2-chloro-4-trifluoromethyl-5-thiazolecarboxylate when component (III) is 2',6'-diethyl-N-(methoxymethyl)-2-chloroacetanilide; 2',6'-diethyl-N-(butoxy-methyl)-2-chloroacetanilide; 2'-ethyl-6'-methyl-N-tethoxymethyl)-2-chloroacetanilide or 2'-ethyl-6'-methyl-N-(1-methoxyprop-2-yl)-2-chloroacetanilide.
65. Emulsion according to claim 47, 48 or 49, which further contains an antidote of 3-(2'5'-dimethoxyphenacyl)-phthalide or ethyl 5-(2,4-dichlorophenyl)-4-isoxazole-carboxylate when component (III) is 2'6'-diethyl-N-(butoxy-methyl)-2-chloroacetanilide.
66. Emulsion according to claim 47, 48 or 49, which further contains an antidote of .alpha.-(cyanomethoxyamino)-benzacetonitrile when component (III) is 2'-ethyl-6'-methyl-N-(1-methoxyprop-2-yl)-2-chloroacetanilide.
67. Emulsion according to claim 47, 48 or 49 which further contains an antidote of N,N-diallyl-2,2-dichloroacetamide when component (III) is S-ethyl di-n-propylthiocarbamate or S-ethyl diiosbutylthiocarbamate.
68. A method of controlling the growth of undesired vegetation comprising applying to the locus to be treated an effective amount of the emulsifiable concentrate of claim 5.
69. A method according to claim 68 wherein the locus to be treated is selected from the group consisting of corn, soybeans and snapbeans.
70. A method according to claim 68 wherein the emulsifiable concentrate is applied at a rate of 2.5 lbs/acre to 4.0 lbs/acre.
71 A method of controlling the growth of undesired vegetation comprising applying to the locus to be treated an effective amount of the emulsifiable concentrate of claim 11, 18 or 22.
72. A method of controlling the growth of undesired vegetation comprising applying to the locus to be treated an effective amount of the emulsifiable concentrate of claim 38 or 47.
73. A method of controlling the growth of undesired vegetation comprising applying to the locus to be treated an effective amount of the emulsifiable concentrate of claim 45 or 46 wherein component (III) is a thiocarbamate having the formula R4S? - N(R5)2 wherein R4 is a C1-4 alkyl or di- or trichloroallyl radical and R5 is a C1-4 alkyl radical.
74. A method of controlling the growth of undesired vegetation comprising applying to the locus to be treated an effective amount of the emulsifiable concentrate of claim 45 or 46 wherein component (III) is a compound having the formula wherein R6 is a C1-4 alkyl radical.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2475379A | 1979-03-28 | 1979-03-28 | |
| US24,753 | 1979-03-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1170856A true CA1170856A (en) | 1984-07-17 |
Family
ID=21822220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000348806A Expired CA1170856A (en) | 1979-03-28 | 1980-03-27 | Emulsifiable concentrate formulations compatible with water and liquid fertilizer |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1170856A (en) |
| GB (1) | GB2049427B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440562A (en) * | 1981-07-20 | 1984-04-03 | Monsanto Company | Herbicidal emulsions |
| CA2047968C (en) * | 1990-08-09 | 2000-05-23 | Paul D. Berger | New surfactant compositions, method for their preparation, and pesticidal compositions containing same |
| DE19752552A1 (en) | 1997-11-27 | 1999-06-02 | Hoechst Schering Agrevo Gmbh | Surfactant systems for liquid aqueous preparations |
| DE10325199A1 (en) * | 2003-06-04 | 2004-12-23 | Clariant Gmbh | Preparations containing amine oxides and anionic surfactants |
| DE602005011618D1 (en) * | 2004-07-15 | 2009-01-22 | Akzo Nobel Nv | PHOSPHATED ALKANOL, ITS USE AS HYDROTROP AND CLEANING COMPOSITION WITH THE COMPOUND |
| WO2011080207A1 (en) | 2009-12-30 | 2011-07-07 | Akzo Nobel Chemicals International B.V. | The use of a phosphated 2-propylheptanol ethoxylate as a bioefficacy enhancer, and a composition containing the phosphated 2-propylheptanol ethoxylate |
-
1980
- 1980-03-27 GB GB8010316A patent/GB2049427B/en not_active Expired
- 1980-03-27 CA CA000348806A patent/CA1170856A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2049427B (en) | 1983-11-16 |
| GB2049427A (en) | 1980-12-31 |
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Effective date: 20010717 |