STABILIZER ADDITIVE FOR AGCHEMICAL TANK MIX
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a stabilizer additive composition for a tank mix of an agricultural chemical, and, more particularly, to a stabilizer additive composition which will inhibit crystal formation therein.
2. Description of the Prior Art
In a diluted tank mix of an agchemical, especially a mix in a highly diluted state at which the emulsifier therein is below its critical micelle concentration, it is observed that the agchemical will precipitate from the mix and affect the delivery of the solution through the spray nozzle.
Accordingly, it is the object of this invention to provide a stabilizer additive composition for a highly diluted tank mix of an agchemical, which can inhibit such unwanted crystal formation in the mix.
SUMMARY OF THE INVENTION
A stabilizer additive composition for a diluted tank mix of an agricultural chemical which will inhibit crystal formation therein when present in an amount of about 0.05-1% by volume of the mix, comprising by weight,
(a) about 5-50% of a water insoluble polymer of vinyl pyrrolidone which is > 30% alkylated with a C4-C2 alkyl group, and has an HLB < 18;
(b) about 10-90% of dodecyl or octyl pyrrolidone, or mixtures thereof, having a CMC of < 0.01% at R.T., and an HLB of about 2-8; and
(c) about 5-40% of an anionic surfactant.
DESCRIPTION OF THE INVENTION
In accordance with the invention, there is provided herein a stabilizer additive composition for a diluted tank mix of an agricultural chemical which will inhibit crystal formation therein when present in an amount of about 0.05-1% by volume of the mix, comprising by weight,
(a) about 5-50% of a water insoluble polymer of vinyl pyrrolidone which is > 30% alkylated with a C4-C2 alkyl group, and has an HLB < 18;
(b) about 10-90% of dodecyl or octyl pyrrolidone, or mixtures thereof, having a CMC of < 0.01% at R.T. , and an HLB of about 2-8; and
(c) about 5-40% of an anionic surfactant.
In preferred forms of the invention, a stabilizer additive composition wherein (a) is about 10-30%; (b) is about 40-80%; and (c) is about 10-30%, also wherein (a) is about 20%; (b) is about 60%; and (c) is about 20%. And a stabilizer additive composition wherein (c) is a dodecyl benzene sulfonate and wherein (b) is dodecyl pyrrolidone.
Suitable anionic surfactants include phosphate esters and their salts, alkyl sulfonamides, salts of sulfated nonylphenoxypoly (ethyleneoxy) ethanol, salts of sulfated tristyryl phenyl (ethyleneoxy) ethanol salts of alkylbenzene sulfonates, salts of alkylnaphthalene
sulfonate, sulfonated aliphatic polyesters and their salts and other aliphatic sulfonated surfactants. Also suitable are complex phosphate esters of nonionic surfactants of the ethylene oxide type which are mixtures of diesters of phosphoric acid (see, for example, McCutcheon's, Emulsifiers and Deteroents (1989) , published by McCutcheon's Division of M.C. Publishing Co., Glen Rock, New Jersey.) Some specific examples of such anionics include sodium dodecyl sulfate (SDS) , sodium dodecyl benzene sulfonate (LAS) , calcium dodecyl benzene sulfonate, ethoxylated nonyl phenol phosphates (RE 610) , etc.
As used herein, the term "agriculturally active chemical" includes compounds and mixtures thereof which can be used as agricultural fertilizers, nutrients, plant growth accelerants, herbicides, plant growth controlling chemicals, and chemicals which are effective in killing plants, insects, microorganisms, fungi, bacteria and the like which are commonly referred to as insecticides, bactericides, fungicides, nematocides, fumigants, and the like, as well as any other chemicals having properties which are suitable for agricultural uses in terms of application to plants or domestic uses for controlling insects and pests. Particularly, such chemicals would normally take the form of water-immiscible or oily liquids and/or solids which are substantially insoluble in water. By the term "substantially insoluble" or "water insoluble", it is meant that for all practical purposes, the solubility of the compound in water is insufficient to make the compound practicably usable in an agricultural end use without some modification either to increase its solubility or dispersability in water, so as to increase the compound's bioavailability or avoid the use of excessively large volumes of solvent.
Suitable agriculturally active chemicals which can be used with the present invention include insecticides, such as, cycloco pounds, carbamates, animal and plant derivatives, synthetic pyrethroids, diphenyl compounds, non- phosphates, organic phosphates, thiophosphates, and dithiophosphates. (See Agricultural Chemicals, Book I, Insecticides, 1989 Revision by W.T. Thomson, Thomson Publications.) typical of the insecticides are: Cyclo compounds: (s)-α-cyano-M-phenoxybenzyl (IR, 3R) -3- (2,2-dibromovinyl)
2,2-dimethyl cyclopropane-carboxylate (DELTAMETHRIN) ; 6,7,8,9,10, 10-hexachloro-l, 5 , 5a, 6 , 9 , 9a-hexahydro-6 , 9- methano-2 , 4 , 3-benzodioxathiepin-3-oxide
Carbamates:
2-isopropyl phenyl-N-methyl carbamate;
2- (1 , 3-dioxolan-2-yl) phenylmethyl carbamate
2, 3-isopropylidine dioxyphenyl methyl carbamate
Animal & Plant Derivatives chlorinated hydrocarbons derived from Southern pine naturally occuring lactone glycoside
Synthetic Pyrethroids: α-cyano-3-phenoxybenzyl cis, trans 3- (2 , 2-dichloro- vinyl) -2,2-dimethyl cyclopropane carboxylate; cyano (3-phenoxyphenyl) methyl-4- (difluoromethoxy)
1-methylethyl) enzene acetate;
Phenoxy Compounds and Non-Phosphate:
2,2-bis(p-methoxy phenyl) -1,1, 1, tri-chloroethane;
1, 3, 5, tri-n-propyl-1,3, 5-triazine-2 , 4 , 6 (1H,3H,5H) trione; ethyl (2E, 4E) -3 , 7 , ll-trimethyl-2 , 4-dodeca dienoate;
1-decycloxy 4-[ (7-oxa-oct-4-ynyl) ] -oxybenzene;
Organic Phosphates: dimethyl phosphate ester of 3-hydroxy-N,N-dimethyl-cis- crotonamide;
2-chloro-l-(2,4-dichloro phenyl) vinyl diethylphosphate;
4- (methyl thio) phenyl dipropyl phosphate;
Thiophosphates :
0, 0-diethyl-0-4-nitrophenyl phosphorothioate;
0, 0-diethyl-O- (2 , isopropyl-6-methyl-5-pyrimidinyl) phosphorothioate ?
2-diethylamino-6-methyl pyrimidine-4-yl dimethyl phosphorothioate ;
Dithiophosphates :
0,0-dimethyl phoεphorodithioate ester of diethylmercapto succinate;
O-ethyl-S-phenyl ethyl phosphorodithioate.
Typical herbicides include phenoxy compounds, benzoic, acetic, and phthalic acids, aniline derivatives, nitriles, amides, acetamides, anilides, carbamates, thio- carbamates, and heterocyclic nitrogen derivatives, e.g., triazines, pyridines, pyridazones, picolinic acid, and urea derivates and phosphates. (See Agricultural Chemicals. Book II, Herbicides. 1986-87 Edition, W.T. Thomson, Thomson Publications, Fresno, CA 93791.) Exemplary of the above compounds are:
Phenoxy Compounds :
2 , 4-dichlorophenoxy acetic acid 2 , 4 , 5-trichloro phenoxyacetic acid;
4-(2,4-dichlorophenoxy) butyric acid;
S-ethyl 2 methyl-4-chlorophenoxythioacetate;
2-methyl-4-chloro-phenoxy acetic acid; methyl 5- (2, 4-dichloro-phenoxy-2-nitrobenzoate;
Benzoic and Acetic Acids of Phthalic Compounds:
3 , 6-dichloro-o-anisic acid 4-chloro-2-oxo benzothiazolin-3- yl acetic acid;
N-1-Naphthyl-phthalamic acid;
Nitriles and Aniline Derivatives:
3-5-dibromo-4-hydroxybenzo-nitrile; α , α , α , trifluoro-2 , 6-dinitro-N, N-dipropyl-p-tolinidine;
N- (1-ethylpropyl) -2, 6-dinitro-3 , -xylidine;
Amides, Acetamides, Anilides:
N,N-diethyl-2-(l-naphthalenyl oxy) -propionamide;
2 , 6-dimethyl-N-2 ' methoxy-ethyl-chloro-acetanilide;
3' , '-dichloro-propionanilide; α-chloracetlc-N- (3 , 5, 5-trimethyl-cyclohexen-l-yl) -N- isopropyla ide ;
4-benzyl-N-isopropyl tri ethyl acetamide;
Thiocarbamates :
S-Ethyl dipropyl thiocarbamate;
Urea Derivatives:
3- (5-tert-butyl-3-isoxazoyl) -1, 1-dimethyl urea;
N- ( 2 , 6-trifluoro-benzoyl) -N' - [ 2 , 5-dichloro-4- ( 1,1,2,3,3,3- hexafluoropropyloxy) phenyl] urea;
Pyrrolidone Derivatives:
1- (m-trifluoro methyl phenyl) -3-chlorσ-4-chloromethyl-2- pyrrolidone;
Amino Acid Derivatives: methyl N-benzoyl-N- (3-chloro-4-fluorophenyl) -DL alarinate;
N-chloroacetyl-N-(2, 6-diethylphenyl) -glycine ethyl ester;
Carbamates :
Isopropyl-m-chlorocarbanilate;
3-Ethoxy (carbonyl aminophenyl) -N-phenyl carbamate;
Heterocyclics :
4-amino-3 , 5-dichloro-6-fluoro-2-pyridyloxy acetic acid;
4-(l,2-Dimethyl-N-propyl amino) -2-ethyl amino-6-methyl thio-
S-triazine;
2- [4 , 5-dihydro 4-methyl-4- (1-methylethyl) -5-oxo-l H- imidazoyl-2yl-3-byridinecarboxylic acid;
2- [ 3 , 5-dichlorophenyl) -2- (2 , 2 , 2-trichloroethyl) oxinane;
Butyl-9-hydro-fluorene-(9) -carboxylate;
2-[l-(ethoxy imino) butylj-3-hydroxy-5-(2H-tetra hydro thiopyran-3-yl) -2-cyclohexene-ione;
2-(2 chlorophenyl) methyl-4 , 4-dimethyl-3-iso oxazolidinone;
Phosphates:
0-ethyl-O- (3-methyl-6-nitro phenyl) N-sec-butyl phosphoro thio amidate.
Typical fungicides include (See Agricultural Chemicals . Book IV, Fungicides. 1989 Revision, W.T. Thomson, Thomson Publications, Fresno, CA 93791) :
Organic Compounds:
2 , 5-dimethy1-N-Cyclohexyl-N-methoxy-3-furan carboxamide ;
N- (4-tert-butylbenzyl) -4-chloro-3-ethyl-l-methylpyrazole-5- carboxamide (TEBUFENPYRAD) ;
5-Ethyoxy-3-trichloromethyl-l, 2, 4-thiadiazole;
3-(2-methyl piperidino) propyl 3,4-dichlorobenzoate;
N,N'-(1, 4-piperazinediyl bis (2, 2 , 2-trichloro) ethylidene) bis formamide;
Tetramethyl thiuram disulfide;
0-Ethyl-S,S,diphenyl-dithiophosphate;
5, 10-dihydro-5,10-dioxo naphtho (2, 3 , 9) -p-dithiin-2, 3- dicarbonitrile;
2-(Thiocyano methyl thio) benzothiazole; α-2-(4-chlorophenyl) ethyl ] -α- ( 1, l-dimethyl ethyl)-l H-
1,2, 4-triazole-l-ethanol;
Morpholines:
N-tridecyl-2 , 6-dimethyl morpholine ;
4-N-dodecyl-2 , 6-dimethyl morpholine;
Typical fumigants, growth regulators, repellants, and rodenticides include (See Agricultural Chemicals. Book III, Fumigants. 1988-1989 Revision, W.T. Thomson, Thomson Publications, Fresno, CA 93791) :
Growth Regulants:
1 , 2 Dihydro-6-ethyoxy-2 , 2 , 4-trimethylquinoline ;
(2-chloroethyl) phosphoric acid;
4-[acetamino methyl] -2-chloro-N- (2 , 6-diethyl phenyl acetamide;
Benzoic acid, 3,6 dichloro-2-methoxy, 2-ethoxy-l-methyl-2-oxo ethyl ester;
Repellants:
0, 0-dimethyl-0-[ (4-methyl thio) -m-tolyl] phosphorothioate;
Tertiary butyl-sulfenyl dimethyl dithio carbamate;
Seed Softener:
2-chloro-6-(trichloromethyl) pyridine; 5-ethoxy-3-trichloromethyl-l , 2 , 4-thiadiazole; N-phenyl-N'-l,2,3-thiadiazol-5-yl urea;
Pesticides may be characterized by their physical properties, depending on their physical state at normal or ambient conditions, i.e., between 40°F. and 90°F. and their solubility or miscibility with water or other common organic solvents, e.g., aromatics, such as, toluene, xylene, methylated and polyalkylated naphthalenes, and aliphatic solvents.
Based on the physical properties, the pesticides may be classified into two groups. The first group includes those which are oily liquids at ambient temperatures and are immiscible with water. Specific pesticides include: Common esters of 2 , 4-dichlorophenoxyacetic acid, Common esters of 2 , 4 , 5-trichlorophenoxyacetic acid, Common esters of 2- (2, 4-dichlorophenoxy) propionic acid, Common esters of 2- (2, 4 , 5-trichlorophenozy) propionic acid, Common esters of 2 , 4-dichlorobutyric acid, Common esters of 2 ,methoxy-3 , 6-dichlorobenzoic acid, Common esters of 2-methyl-4-chlorophenoxyacetic acid, Piperonyl butoxide 3 , 4-methylenedioxy-6-propyl benzyl n-butyl diethylene glycol ether,
Bromophos ethyl: 0,0-diethyl-0-2,5-dichloro-4-bromophenyl thionophosphate,
N-(2-mercaptoethyl) benzene-sulfenamide (BETASAN®) , Isobornyl Thiocyanoacetate (Thanite®) , Ioxynil ester of octanoic acid,
Molinate S-ethyl hexahydro - 1 H - azepine-1-carbothioate, PP 511 0, 0-dimethyl-(2-diethylamine 4-methyl-6-pyrimidinyl) carbamate,
PP 211 0,0-diethyl 0-(2-diethylamine-4-methyl-6-pyrimidinyl) phosphorocarbamate , Chlordane,
5-Ethoxy-3-(trichloromethyl) -1, 2 , 4-thiadiazole (TERRAZALE®) , Ethyl-s-s-dipropyl-phosphodithioate (MOCAP®) ,
S-Ethyl dipropylthiocarbamate (EPTAM®) ,
S-Ethyl diisobutylthiocarbamate (SUTAN®) ,
S-n. propyl-di-n-propylthiocarbamate (VERNAM®) ,
S-propyl butylethylthiocarbamate (TILLAM®) ,
5-ethyl ethylcyclohexylthiocarbamate (RO-NEET®) ,
Malathion (S-(l,2-dicarboxyethyl)-0, 0-dimethyl phosphoro- dithioate) ,
Diazinon (0, 0-diethyl, 0- (2-isopropyl-4-methyl-6-pyrimidinyl) phosphorothioate,
O-Ethyl-S-phenyl-ethylphosphonodithioate (DYFONATE®) ,
Toxaphene (Octachlorocamphene) ,
Bro oxynil (3 , 5-dibromo-4-hydroxy benzonitrile ester of n.octanoic acid,
2-chloro-N-2 , 6-diethylphenyl-N-methoxymethylacetamide
(LASSO®) ,
Diallate S-2 , 3-dichloroallyl N,N-diisopropylthiol-carbamate,
Triallate S-2 , 33-trichloroallyl N,N-diisopropylthiol- carbamate.
The second group comprises those pesticides which are solids at ambient temperatures and for all practical purposes, insoluble in water. 2,4, 5-T (2 ,4 , 5-trichlorophenoxy acetic acid) Monuron (3-(p-chlorophenyl) -1, 1-dimethyl urea) Diuron (3- (3 , 4-dichlorophenyl) -1, 1-dimethyl urea) Bromacil (5 bromo-3-sec. butyl-6-methyl uracil) Isocil (5 bromo-3-isopropyl-6-methyl uracil) Linuron (3- (3, 4 dlchlorophenyl) -1-methoxy-l methyl urea Atrazine (2-chloro-4-ethylamino-6 isopropylamino-s-triazine) Simazine (2-chloro-4 , 6, -bis (ethyla ino) -s-triazine Dodine (n-dodecylguanidine acetate)
Thiram (tetramethylthiuram disulfide)
N-(mercaptomethyl)phthalimide s-(o,o dimethylphosphoro- dithioate) (IMIDAN®)
Lindane (gamma 1,2,3,4,5,6 hexachlorocyclohexane)
Folpet (N-trichloromethylphthalimide)
Manazon (s- (4, 6-diamino-l, 3, 5-triazin-2-yl methyl) di ethylphosphorothiolthionate)
Barban (4-chloro-2 butynyl m-chlorocarbanilate)
Tricumba 2-methoxy-3, 5, 6-trichlorobenzoic acid
Trifluralin (2, 6-dinitro-N,N-dipropyl-4-trifluoro- methylamiline) (2,3 dihydro-5-carboxanilido-6-methyl-
1,4-oxathiin) (VITAVAX®)
2 , 4-dichlorophenoxyacetic acid
4-(4-chloro-2 methylphenoxy) butyric acid
2- (2, 4-dichlorophenoxy) propionic acid
Ioxynil: 3,5 diiodo-4-hydroxybenzonitrile
Bromoxynil: 3,5 dibromo-4-hydroxybenzonitrile
Carbaryl : 1-naphthyl-N-methylcarbamate
Methoxychlor : 2,2, -Bis (p-methoxyphenyl) -1 , 1-trichloro-ethane
PP 781: 4(2-chloro phenylhydrazono) -3-methyl-5-isoxazolone*
PP 675: 5-butyl-2-dimethylamino-4-hydroxy-6-methyl pyrimidine*
PP 062: 5,6-dimethyl-2-dimethylamino-4 pyrimidinyl dimethylcarbamate*
PP 149: 5-n-butyl-2 ethylamino-4-hydroxy-6 methylpyrimidine*
C 6313 N'- (4-bromo-3-chlorophenyl) -N-methoxy-N-methylurea
C 6989 2 ,4'dinitro-4-trifluoromethyl-diphenylether
Chloroxuron N'-4-(chlorophenoxy) phenyl-NN-dimethylurea
Dichlobenil 2 , 6-dichlorobenzonitrile
Diphenamid NN-dimethyl-2 , 2-diphenylacetamide
* Manufacturd by Imperial Chemical Industries Limited
Fenac 2, 3,6-trichlorophenylacetic acid
Fluometuron N'-(3-trifluoromethylphenyl) -NN-dimethylurea
GS 14260 4-ethylamino-2-methylthio-6-t-butyl-amino-l, 3 ,5- triazine
PCP Pentachlorophenol
Lenacil 3-cyclohexyl-6 , 7-dihydro-lH-cyclo-pentapyrimidine-
2,4-(3H,5H)-dione
Pyrazon 5-amino-4-chloro-2-phenyl-3-pyridazone
Metrobromuron N' - (4-bromopheny1) -N-methoxy-N-methylurea
Metoxymarc N- (4- ethoxybenzoy1) -N- (3,4-dichloropheny1) -
N' , N' -dimethylurea
Neburon N-butyl-N'- (3 , 4-dichloropheny1-N-methylurea
NIA 11092 1, l-dimethyl-3-[3-(n-t-butyl carbamyloxy) phenyl] urea
Mecoprop 2- (4-chloro-2 methylphenoxy) ropionic acid
Monolinuron N' - (4-chlorophenyl) -N-methoxy-N-methylurea
Nitrofen 2 , 4-dichlorphenyl 4-nitrophenylether
Propanil N-(3 ,4-dichlorophenyl)propionamide
Pyriclor 2,3, 5-trichloro-4-pyridinol
Solan 3 ' -chloro-2-methyl-p-volerotoluidide
Terbacil 5-chloro-3-t-butyl-6-methyluracil
UC 22463 (SIRMATE)-3,4-dlchlorobenzyl N-methylcarbamate
WL 9385 2-Azido-4-ethylamino-6-t-butylamino-s-triazine
Propachlor 2-chloro-N-isopropylacetanilide
CP 50144 2-chloro-N-2, 6-diethylphenyl-N-methoxymethyl acetamide
CP 31675 2-chloro-N- ( 2 methyl-6-t-butylphenyl) acetamide
Cypromid 3 ' , 4 ' -dichlorocyclopropane carboxanilide
Fenuron NN-dimethyl-N ' pheny lurea
Chlorbromuron N' - ( -bromo-3 -chlorophenyl) -N-methoxy-N-methyl urea
Ametryne 2-methylmercapto-4-ethylamino-6-isopropyl-amino-s- triazine
Prometryne 2-methylmercapto-4 , 6-bisisopropyl amino-s- triazine
DCPA dimethyl 2,3,5,6, tetrachloroterephthalate
Benefin N-butyl-N-ethyl-2 , 2 , 2-trifluoro-2 , 6-dinitro-p- toluidine
Nitralin 2, 6-dinitro-4-methylsulfonyl-NN-dipropyl-aniline
PP 493 2,6-difluoro-3, 5-dichloro-4-hydroxy pyridine
CNP 2,4 , 6-trichlorophenyl-4'-nitrophenyl ether
Pentachloro nitrobenzene l-(butile carbamoyl) -2-benzimidazol carbamic acid, methyl ester (BENLATE®)
It is to be understood that mixtures of the above agrichemicals can be used to reinforce function or to serve multiple functions, e.g. as an insect repellent and plant growth regulant or any other combination of functions.
Generally, about 0.05 to 0.1% by volume of the stabilizer additive composition of the invention is added to the diluted tank mix.
The invention composition inhibits crystal formation for greater than 16 hours at a 0.05% level.
EXAMPLES A stabilizer additive composition was prepared as follows:
Agrimer AL 22 (ISP)* 20 g
Agsol Ex 12** 60 g
Rhodacal 60 BHT*** 20 σ
100 g
* polymer of vinyl pyrrolidone alkylated with C16 alkyl group 20% vinyl pyrrolidone - 80% alkyl group, HLB 3-5.
** dodecylpyrrolidone
*** calcium dodecyl benzene sulfonate
Then 0.05% of the composition was added to a tank mix of an Fipronil® (Rhone-Poulenc) pyrazole insecticide, emulsifiable concentrate (EC)**** diluted in 3 liters of 1000 ppm of hard water (0.03% active). After free-standing for 16 hours, the dilutions were filtered through Spectra/Mesh 41μm nylon filters. The residue from the dilution with the invention adjuvant was equivalent to the residue from the control (1000 ppm water) . Thus, there were no Fipronil crystals when this additive was used in the tank mix. These results can be seen in Figure 1.
Similar tests were done, but the dilutions were stored with vigorous shaking. Under these conditions, the dilution with 0.1% addition of the invention adjuvant showed no evidence of crystallization for greater than 16 hours. In contrast, the dilution with no adjuvant showed crystals in one hour, whereas the dilution with 0.05% invention adjuvant retarded crystals for 4 hours. These results can be seen in Figure 2. An optical microscope with cross- polarization was used to search for crystals, using up to 500X magnification on diluted specimens.
After 16 hours of vigorous shaking, these dilutions were filtered as previously described. The dilution with no adjuvant showed the greatest residue on the filter, while the dilutions with added adjuvant showed about 3 times less residue on the filters. These results can be seen in Figure 3.
The microscopy and filtration experiments show that using the invention stabilizer additive composition at 0.05% to 0.1% prior to EC addition, retards crystallization for more than 16 hours.
**** Fipronil EC of active, solvents and emulsifiers
In summary, the invention composition is most effective when added to the tank mix rather than added to the active EC followed by dilution.
While the invention has been described with particular reference to certain embodiments, it is to be understood that many substitutions, alterations and modifications can be made therein which are also considered to be within the scope of this invention.