Patent Publication Number: US-11382327-B2

Title: Emulsifiable concentrate of tefluthrin

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a 371 National Stage application of International Application No. PCT/EP2017/063498, filed Jun. 2, 2017, which claims priority to U.S. Patent Application No. 62/348,059 filed Jun. 9, 2016 and Great Britain Application No. 1611288.0 filed Jun. 29, 2016, the entire contents of which applications are hereby incorporated by reference. 
    
    
     TECHNICAL FIELD 
     The present invention relates to an emulsifiable concentrate composition, to the preparation thereof and to a method of using such a composition to control pests in crops of useful plants. 
     BACKGROUND 
     Tefluthrin (TFT) is a pyrethroid insecticide widely used for corn root worm control via in furrow application at planting. TFT is applied in the form of granules or in the form of a liquid spray solution. In the currently used liquid spray solutions, TFT is formulated as a capsule suspension (CS). The reason for the encapsulation of TFT is the hazardous nature of the pyrethroid insecticides in general, and TFT more specifically. Such steps taken by formulators to reduce operator exposure to TFT may be beneficial in terms of direct operator exposure, however, such steps can result in reduced biological activity and can also lead to physical incompatibility with high ionic strength solutions such as for example liquid fertilizer products. 
     The formulated TFT product is typically applied alongside or via an admixture of liquid fertilizer and formulated product. The application of the admixture of liquid (aqueous) fertilizer and TFT product is problematic in that physical incompatibilities often exist which may lead to poor biological efficacy and/or problematic application of the admixtures. The problematic application of such admixtures manifestates itself in the necessity of extensive cleaning operations of the application equipment after the application has taken place which leads to potential operator exposure of TFT. 
     Thus, there is a need for a formulated TFT product which demonstrates a high degree of physical compatibility with carriers such as water of varying hardness, chemical makeup and temperatures as well as liquid fertilizers while at the same time providing similar or superior efficacy compared to existing commercial formulations. Such a TFT formulation would enable the use of closed delivery systems such as the John Deere CIS and Raven direct injection systems which in turn would decrease the need for manual intervention and cleaning operations thus limiting exposure of operators to TFT. The current invention provides such a novel TFT formulation which exhibits the above benefits. Thus, the current invention provides a novel emulsifiable concentrate which is stable, i.e. does not show phase separation, and is suitable for dilution with water or water-based fertilizers. 
     WO2009/019299 disclose microemulsions, i.e. oil-in-water emulsions where water forms the continuous phase and the average particle size of the oil phase does not exceed 200 nm, of low water-soluble active ingredients. 
     SUMMARY OF THE INVENTION 
     In a first aspect, the current invention provides as embodiment 1 a single-phase emulsifiable concentrate (EC) composition, comprising 
     (i) the pesticide tefluthrin; 
     (ii) a solvent for dissolving tefluthrin; 
     (iii) a water-soluble emulsifying surfactant system enabling an oil in water emulsion to be formed when the emulsifiable concentrate composition is diluted with an aqueous solution; 
     (iv) a non-aqueous polar solvent for diluting the water-soluble emulsifying surfactant system; 
     (v) a C 2 -C 10 -alcohol to provide physical compatibility between (a) hydrophobic component (ii) and (b) hydrophilic components (iii) and (iv). 
     In a second aspect, there is provided an insecticidal composition obtained by diluting the EC compositions according to the first aspect in a suitable carrier, such as water or liquid fertilizer, such that the final concentration of TFT present is between 0.01 weight % and 10 weight % by weight of the total insectidal composition. 
     In a further aspect, there is provided a method for controlling a pest comprising diluting an amount of an EC composition according to the first aspect with a suitable liquid carrier, in particular an aqueous liquid carrier, such as water or liquid fertilizer, and then applying the dilute composition to the plant propagation material, plant or locus thereof. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The term “single-phase” as used herein denotes a single-phase homogenous solution at room temperature (20-25° C.). The visual presence of solids and/or of two distinct liquid phases would be unacceptable non single-phase behavior. 
     The term “emulsifiable concentrate” or “EC” as used herein relates to a concentrated oil-based formulation. Small amounts of water may be present in an EC (&lt;5% by weight) but said water cannot be present as a discrete phase. The ECs are transparent and will only be diluted with water or water-based fertilizers directly before application and form white to off-white dilutes. 
     The term “tefluthrin” or “TFT” as used herein refers to the pesticide with the common name “tefluthrin” having the CAS (Chemical Abstracts Service) registry number 79538-32-2 and chemical abstracts name (2,3,5,6-tetrafluoro-4-methylphenyl)methyl (1R,3R)-rel-3-[(1Z)-2-chloro-3,3,3-trifluoro-1-propen-1-yl]-2,2-dimethylcyclopropanecarboxylate. 
     The term “solvent for dissolving tefluthrin” as used herein means any solvent, or combination of solvents, capable of completely dissolving from 20 to 80 weight % tefluthrin. Examples of suitable solvents include but are not limited to mixtures of aromatic hydrocarbons such as Aromatic/Solvesso® 100, 150, 150ND, 200 and 200ULN (ExxonMobil Chemical), C 4 -C 12  aliphatic methyl or ethyl esters (e.g. Steposol C-25®, Steposol C-40®, Steposol C-42®, Steposol C-48® and Steposol C-65® (Stepan), Agnique ME 610 and Aqnique ME810 (BASF)), methylated seed oil blends such as methylated sobybean oil, methyl oleate/linoleate, palmitate, carboxylic acids (C 4 -C 10 ), ethyl esters (C 4 -C 10 ), aliphatic mineral oils, and mixtures thereof. 
     The term “water-soluble emulsifying surfactant system” as used herein means any emulsifying surfactant system which enables the forming of an oil in water emulsion when the emulsifiable concentrate is diluted with an aqueous solution. Such an emulsifying surfactant system may comprise one or more surfactant. The surfactants may be non-ionic, anionic, cationic or Zwitterionic. Examples of particular suitable surfactants include but are not limited to alkyl polyglycosides, polyalkylene oxide block copolymers and polyaryl-phenyl ether phosphates. 
     Alkyl polyglycosides include Agnique® PG (“APG”) 8107 (Cognis Corporation, Cincinnati, Ohio, USA) (an alkyl polyglycoside in which the alkyl group contains 8 to 10 carbon atoms and has an average degree of polymerization of 1.7), Agnique® PG 9116 (Cognis Corporation, Cincinnati, Ohio, USA) (an alkyl polyglycoside in which the alkyl group contains 9 to 11 carbon atoms and has an average degree of polymerization of 1.6) and Agnique® PG 8105 (Cognis Corporation, Cincinnati, Ohio, USA) (an alkyl polyglycoside in which the alkyl group contains 8 to 10 carbon atoms and has an average degree of polymerization of 1.5). 
     Polyalkylene oxide block copolymers can be di- and tri-block copolymers, such as ABA or BAB block copolymer or BA block copolymers. Examples include the Genapol® PF series (Clariant), the Pluronic® series (BASF), the Synperonic® PE series (Uniqema), and the Toximul® series (Stepan Chemical Co.). A preferred group of ethylene oxide/propylene oxide block copolymers for use in the compositions of this invention are butyl based poly(oxypropylene)/poly(oxyethylene)block copolymers having an average molecular weight in the range of 2400 to 3500, for example Toximul® 8320, Stepan Chemical Co.). Suitable examples include Pluronic® L10, Pluronic® L44, Pluronic® L63, Pluronic® L64, Pluronic® L84, Pluronic® P104, Pluronic® P105, Step-Flow® 26, Toximul® 8323 and Toximul® 8320. 
     Polyaryl-phenyl ether phosphates include ethoxylated tristyrylphenol phosphates such as Soprophor® 3D33 (Rhodia), Soprophor 3D33 LN® (Rhodia), Emulsogen 57® (Clariant), Agnique PE TSP-16A® (BASF), Agrhospec 7822® (Rhodia), Dispersogen TP 160® (Clariant), Stepfac TP 160® (Stepan), Stepfac TSP-PE® (Stepan). The degree of ethoxylation of the polyaryl-phenyl ether phosphates for this purpose is preferably between 8 and 20, more preferably between 14 and 18. 
     The term “non-aqueous polar solvent” as used herein means solvents having Hansen Solubility Parameter (HSP) values greater than 2, in particular greater than 5 and more particularly between 5 and 15. Examples of suitable non-aqueous polar solvents include acetone, amyl acetate, butanol, benzyl alcohol, cetyl alcohol, dimethyl ether, propylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, octanol, hallcomid M-8-10, hexylene glycol, cyclohexanol, ethyl lactate, ethyl alcohol, 2-ethyl hexanol, glycerol monoacetate, glycerol diacetate, glycerol triacetate, 3-hexanol, n-hexyl alcohol, isopropyl myristate, lactic acid, lactic acid 2-ethyl hexyl ester, lactic acid n-propyl ester, methyl alcohol, methyl n-amyl ketone, methyl isobutyl ketone, oleyl alcohol, propanol, tetrahydrofurfuryl alcohol, butyrolactone, chlorobenzene, diacetone alcohol, n-decanol, N,N-dimethyl decanamide, N,N-dimethyl octanamide, dimethyl lactamide, n-decyl alcohol, dipropyleneglycol monomethylether, ethylene glycol monobutyl ether, isobornyl acetate, isobutyl alcohol, mesityl oxide, methyl ethyl ketone, 2-methyl-2,4-pentanediol, N-octyl pyrrolidone, N-methyl pyrrolidone, n-octyl alcohol, oxo-decyl acetate, oxo-heptyl acetate, oxo-hexyl acetate, oxo-nonyl acetate, oxo-octyl acetate, oxo-tridecyl acetate, propylene glycol monomethyl ether, triethylene glycol, triethyl phosphate, lactic acid n-butyl ester, lactic acid ethyl ester, dodecyl pyrrolidone, N,N-dimethyl acetamide, propylene carbonate and mixtures thereof. In particular, the non-aqueous polar solvent is selected from propylene glycol, dipropylene glycol, dipropylene mono-methyl glycol ether and mixtures thereof. 
     As used herein, the term “Hansen Solubility Parameters” (HSP) refers to system of describing solute solubility in a solvent based on the non-polar parameter, polar parameter, hydrogen bonding parameter, and total solubility parameter as disclosed in “Hansen Solubility Parameters” by Charles M. Hansen, ISBN 0-8493-7248-8. For definition of Hh=Hydrogen Bonding Solubility Parameter, see page 17 of the above book. For definition of Hp=Polar Solubility Parameter see page 16-17 of the above book. 
     The term “C 2 -C 10 -monohydric alcohol” as used herein refers to saturated aliphatic straight or branched alcohols with 2 to 10 carbon atoms and having one hydroxyl group. 
     Embodiments 1 to 13 provide preferred embodiments of the invention. It is understood that each preferred embodiment may be combined with one or more of the other preferred embodiments. 
     In embodiment 2, there is provided the single-phase emulsifiable concentrate composition according to embodiment 1, wherein (v) the C 2 -C 10 -alcohol is selected from ethanol, 1-hexanol, 1-octanol and 1-decanol, in particular 1-octanol. 
     In embodiment 3, there is provided the single-phase emulsifiable concentrate composition according to embodiment 1 or 2, wherein (iii) the water-soluble emulsifying surfactant system comprises one alkyl polyglycoside surfactant. 
     In embodiment 4, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 3, wherein (iii) the water-soluble emulsifying surfactant system comprises one polyalkylene oxide block copolymer. 
     In embodiment 5, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 4, wherein (iii) the water-soluble emulsifying surfactant system comprises one polyaryl-phenyl ether phosphate. 
     In embodiment 5.1, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 4, wherein the weight ratio of component (v) to component (iii) in the composition is from 1:1.5 to 1:15, particularly from 1:3 to 1:8, more particularly from 1:4 to 1:6. 
     In embodiment 6, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 5, wherein (iv) the non-aqueous polar solvent is selected from propylene glycol, dipropylene glycol and dipropylene mono-methyl glycol ether, or a mixture thereof. 
     In embodiment 7, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 6, wherein (ii) the solvent for dissolving tefluthrin comprises one aromatic hydrocarbon or one C 6 -C 12 -alkyl-C(═O)—CH 3 , or a mixture thereof. 
     In embodiment 8, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 7, wherein (ii) the solvent for dissolving tefluthrin is a mixture of aromatic hydrocarbons. 
     In embodiment 9, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 8, wherein the weight % of component (v) in the emulsifiable concentrate composition is from 2 to 10 weight %. 
     In embodiment 10, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 9, wherein the weight % of component (v) in the emulsifiable concentrate composition is from 4 to 6 weight %. 
     In embodiment 11, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 10, wherein the combined weight % of components (i) and (ii) in the emulsifiable concentrate composition is from 60 to 80 weight %. 
     In embodiment 12, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 11, wherein the combined weight % of components (i) and (ii) in the emulsifiable concentrate composition is from 65 to 75 weight %. 
     In embodiment 13, there is provided the single-phase emulsifiable concentrate composition according to any one of embodiments 1 to 12, wherein 
     the weight % of components (i) to (v) in the emulsifiable concentrate composition are 
     (i) 20-30 weight %; 
     (ii) 40-50 weight %; 
     (iii) 15-25 weight %; 
     (iv) 2-15 weight %; and 
     (v) 2-10 weight %. 
     The term “compositions of the present invention”, “compositions of the current inventions” or “inventive EC compositions” as used herein mean compositions according to any one of embodiments 1 to 13. 
     The following advantages of the emulsifiable concentrate (EC) compositions of the present invention have been surprisingly found: 
     (a) no separation due to two phase system (oil and water); 
     (b) no sedimentation when EC is diluted with an aqueous solution; 
     (c) excellent physical compatability with liquid fertilizers; 
     (d) storage-stability for extended periods; 
     (e) application in the field possible with closed delivery system such as John Deere CIS and Raven direct injection system, thereby avoiding exposure of operators to the hazardous material; 
     (f) improved cleanout properties: ease of cleaning the delivery system significantly improved compared to current commercial offerings, thereby decreasing the time operators may be exposed to the hazardous material. 
     In a further aspect, the current invention provides a method for controlling a pest comprising diluting an amount of an EC according to any one of embodiments 1 to 13 with a suitable liquid carrier, in particular an aqueous liquid carrier, such as water or liquid fertilizer, and then applying the dilute composition to the plant propagation material, plant or locus thereof. In a particular embodiment, the pest is corn root worm. In another particular embodiment, the dilute composition is applied by in furrow or T-band type application. The composition of the present invention may also be combined in a continuous flow apparatus with water in spray application equipment, such that no holding tank is required for the diluted product. 
     The inventive EC compositions can be stored conveniently in a container from which it is poured, or pumped, or into which a liquid carrier is added prior to application. 
     In another aspect, the invention also relates to insecticidal compositions obtained by diluting the EC compositions according to any one of embodiment 1 to 13 in a suitable carrier, such as water or liquid fertilizer, such that the final concentration of TFT present is between 0.01 weight % and 10 weight % by weight of the total insectidal composition. 
     Other active ingredients such as herbicides, plant growth regulators, algicides, fungicides, bactericides, viricides, insecticides, acaridicdes, nematicides or molluscicides may be present in the EC compositions of the present invention or may be added as a tank-mix partner to the dilute spray compositions prepared therefrom. 
     In addition, the EC compositions of the invention may further comprise other additives. Such additives include safeners, thickeners, flow enhancers, wetting agents, antifoaming agents, biocides, buffers, chelating agents, lubricants, fillers, drift control agents, deposition enhancers, evaporation retardants, frost protecting agents, insect attracting odor agents, UV protecting agents, fragrances, and the like. These additives are known to a person skilled in the art. 
     The liquid fertilizers may comprise, for example, either nitrogen based fertilizers or nitrogen, phosphorous and/or potassium. Examples of liquid fertilizers include but are not limited to 
     10-34-0; 
     2-15-19-3S (Conklin); 
     3-18-18 (Conklin); 
     32-0-0; 
     4-10-10 (Pearl City Elevator); 
     4-10-10 w/zinc 9% EDTA (Pearl City Elevator); 
     4-10-10 w/zinc Triple Crown (Pearl City Elevator); 
     5 parts 8-24-0, 1 part Sidekick (Conklin); 
     8-16-11-2S (Conklin); 
     8-24-0 (Conklin); 
     8-24-4; 
     9-18-9 f(Conklin); 
     Ascend PGR; 
     Aventine; 
     Chadwick Oil and Ag 6-24-6 (¼ Zn); 
     Co-Alliance with Micros; 
     Gavilon 120 LC; 
     Helena Nucleus HyperLink HP 8-24-4; 
     Helena Nucleus 0-Phos 8-24-0; 
     Helena Nucleus Ortho-Phos NPK ZN 7-21-2; 
     Hi-Test Complete Nutritional Starter (8-18-4); 
     HyperLink; 
     HyperLink XL; 
     Insta-Gro 3-18-18-1; 
     Insta-Gro 5-20-5-1; 
     Insta-Gro 9-18-9-1; 
     Mixture of Nresponse (24-0-0-1S), eNhance, and Pro-Germinator (9-24-3) (Agro-culture Liquid Fertilizers); 
     Morral Companies 9-18-9-1S-0.1Zn; 
     Nachurs 6-24-6+S; 
     Nachurs 9-18-9; 
     Nachurs 9-20-3+S; 
     Nachurs G24 (6-24-6); 
     Nachurs LKW20 (9-20-3); 
     Nachurs Upstart (6-20-6); 
     Nachurs W18-S (9-18-9-1); 
     Nutra-Flow GoldStart (6-24-6); 
     P Max Plus (7-20-3); 
     PhosPlus; 
     PhosPlus+9-15-4; 
     Pro-Valley Gold; 
     Redline; 
     RiseR 7-17-3; 
     Twin States Liquibrom; 
     X-Cell Growth Boost; 
     X-Cell MicroNutrient Supplement; 
     The EC compositions of the present invention may be prepared by charging a solvent (ii) according to embodiment 1 into a vessel, then charging solvent (v) according to embodiment 1 to the same vessel and mixing until homogenous, then adding the TFT solution followed by solvent (iv) according to embodiment 1 and mixing the whole until homogenous. The water-soluble emulsifying surfactant system (iii) according to embodiment 1 is then added and the whole mixed until homogenous. 
     The following examples illustrate further the invention but are not intended to limit its scope. 
     Experimental 
     Formulation Preparation: 
     
         
         
           
             1. Charge aromatic fluid to vessel. 
             2. Charge n-octanol to the vessel and mix until homogenous. 
             3. Charge pre-heated (50° C.) dissolved TFT to the vessel and mix until homogenous. 
             4. Charge dipropylene glycol and mix until homogenous. 
             5. Charge pre-heated Toximul 8320 (40-50° C.) and mix until homogenous. 
             6. Charge pre-heated Soprophor 3D33 (40-50° C.) and mix until homogenous. 
             7. Charge pre-heated Agnique PG-8107 (40-50° C.) and mix until homogenous.
 
(a) Separation Due to Two Phase System (Oil and Water):
 
           
         
       
    
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 The following EC formulations 1-4 were prepared. The total weight  
               
               
                 for each batch was 20 grams. 
               
            
           
           
               
               
            
               
                   
                 Components (Function) 
               
            
           
           
               
               
               
               
               
            
               
                   
                 1 
                 2 
                 3 
                 4 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 TFT in Aromatic 100 ® (Active ingredient) 
                 1.6 
                 1.6 
                 2.0 
                 2.0 
               
               
                 Toximul ® 8320:Soprophor ® 3D33 -= 1:2  
                 1.9 
                 1.4 
                 1.5 
                 1.0 
               
               
                 (Emulsifiers) 
                   
                   
                   
                   
               
               
                 Dipropylene glycol (Non-aqueous polar  
                 1.5 
                 2.0 
                 1.5 
                 2.0 
               
               
                 solvent) 
                   
                   
                   
                   
               
               
                 Agnique ® 8107 (Emulsifier) 
                 15.0 
                 15.0 
                 15.0 
                 15.0 
               
               
                 Total weight (grams) 
                 20 
                 20 
                 20 
                 20 
               
               
                   
               
            
           
         
       
     
     Formulations 1-4 showed turbidity and the two phases (oil and water) separated after a short time. Comparison testing was carried out on formulation 4 above in order to solve the phase separation problem. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Comparison testing on formulation 4. 10 grams of formulation 4 were  
               
               
                 taken for each comparison test. Solvents were added in increments of  
               
               
                 0.25 grams up to maximum of 2 grams or until cloudiness of formulation  
               
               
                 cleared. Phase separation was checked 1 hour and 72 hours after the  
               
               
                 addition of the solvents. 
               
            
           
           
               
               
               
               
            
               
                 Solvent Added 
                 Cloudiness 
                 0 C (1 hr) 
                 0 C (72 hr) 
               
               
                   
               
               
                 Dipropylene glycol 
                 Does not clear 
                 Not tested 
                 Not tested 
               
               
                 Rhodiasolv ® RDPE 
                 Clear at + 1.25 g 
                 Phases  
                 Not tested 
               
               
                   
                   
                 separated 
                   
               
               
                 Stepan C25 ® 
                 Clear at + 1.50 g 
                 Phases  
                 Not tested 
               
               
                   
                   
                 separated 
                   
               
               
                 1-Hexanol 
                 Clear at 0.25 g 
                 Clear 
                 Clear 
               
               
                 Solvent Added 
                 Cloudiness 
                 0 C (1 hr) 
                 0 C (72 hr) 
               
               
                 1-Octanol 
                 Clear at + 0.25 g 
                 Clear 
                 Clear 
               
               
                 1-Decanol 
                 Clear at + 0.25 g 
                 Clear 
                 Clear 
               
               
                 Dipropylene glycol 
                 Clear at + 0.75 g 
                 Phases  
                 Not tested 
               
               
                 monomethyl ether 
                   
                 separated 
                   
               
               
                 Rhodiasolv ® Polarclean 
                 Clear at + 1.0 g  
                 Phases  
                 Not tested 
               
               
                   
                   
                 separated 
                   
               
               
                 Dimethyl glutarate 
                 Clear at + 1.25 g 
                 Phases  
                 Not tested 
               
               
                   
                   
                 separated 
                   
               
               
                 Propylene glycol 
                 Does not clear 
                 Not tested 
                 Not tested 
               
               
                   
               
            
           
         
       
     
     It was found that the hydrophilic and hydrophobic phases surprisingly do not separate after 1 hour and 72 hours when 1-hexanol, 1-octanol and 1-decanol was added to the EC. 
     (b) Sedimentation when EC is Diluted with an Aqueous Solution: 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Formulations 5-8 were prepared due to the findings under (a). The  
               
               
                 composition is given as weight % of the total weight of the composition. 
               
            
           
           
               
               
            
               
                   
                 Components (Function) in  
               
               
                   
                 weight % 
               
            
           
           
               
               
               
               
               
            
               
                   
                 5 
                 6 
                 7 
                 8 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 TFT (Active ingredient) 
                 25.00 
                 25.00 
                 25.00 
                 25.00 
               
               
                 Aromatic 100 ® (solvent) 
                 44.69 
                 44.69 
                 45.00 
                 45.00 
               
               
                 Dipropylene glycol 
                 9.50 
                 7.00 
                 7.50 
                 5.00 
               
               
                 1-Octanol 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
               
               
                 Agnigue ® 8107 (Emulsifier) 
                 7.50 
                 10.00 
                 7.50 
                 10.00 
               
               
                 Toximul ® 8320 (Emulsifier) 
                 2.78 
                 2.78 
                 3.33 
                 3.33 
               
               
                 Soprophor ® 3D33 (Emulsifier) 
                 5.53 
                 5.53 
                 6.67 
                 6.67 
               
               
                 Total 
                 100 
                 100 
                 100 
                 100 
               
               
                   
               
            
           
         
       
     
     Dilution tests: Formulations 1-8 are diluted at 5% v/v in a 100 ml (milliliter) graduated cylinder using water with a water hardness of 1000 ppm. Samples are checked periodically for sedimentation or phase separation and then re-homogenized after 24 hrs. Re-homogenization is recorded as the number of cylinder inversions needed to re-suspend all separated material. Re-suspension effort is checked again after another 72 hours to check for long term compatibility. The results are shown in Table 4. 
                     TABLE 4                  After dilution with water, the samples were checked for sedimentation or phase separation       (scale of 0-3, 0 indicating no sedimentation or phase separation and 1-3 indicating sedimentation or       phase separation, 1 being least sedimentation/phase separation to 3 most) at 1, 3, 18 hours after       dilution and then after 72 hours.                                                             Sedimentation       Sedimentation   Inversions       Inversions to           1       or phase   18   or phase   to Re-   72   Re-       Formulation   hour   3 hours   separation   hours   separation   homogenize   hours   homogenize               1   1   2   sediment   2   sediment   2   2   2       2   1   1   sediment   2   sediment   2   2   2       3   1   2   sediment   2   sediment   2   2   3       4   1   2   sediment   2   sediment   2   2   2       5   0   Not   Not tested   Trace   Phase   1   1   1               Tested           separation       6   0   Not   Not tested   Trace   Phase   1   1   1               Tested           separation       7   0   Not   Not tested   Trace   Phase   1   1   1               Tested           separation       8   0   Not   Not tested   Trace   Phase   1   1   1               Tested           separation                    
(c) Physical Compatability with Up to 40 Liquid Fertilizers:
 
     Formulation 9, which is the same as formulation 8 above only that Aromatic 100® has been replaced with Aromatic 150®, and the current commercial aqueous capsule suspension product (formulation 10) have been tested for compatibility with a large range of liquid fertilizers. The procedure for this compatibility test was as follows: 
     1) 150 ml of liquid fertilizer was added into a glass jar. 
     2) 12 ml (about 2% v/v) of formulations 9 and 10 were added into the glass jar. 
     3) Samples were inverted 10 times. 
     4) Separation, sediment, flocculation, etc., was observed. 
     Dynamic Test: 
     5) The formulation was shaken for 1 hour at 375 cycles per minute. 
     6) Remove samples from shaker and allow to suit undisturbed at least for 2 minutes but no longer than 10 minutes. Visual observations such as sediment, flocculation, separation of layers, scum on jar sides, etc. 
     7) Jars were then shaken and the contents poured through stacked 50 and 100 US standard mesh screens. 50 ml of water was then added into the jars, recapped, shaken and poured through the screens. The type and amount of any residue on jar and/or screen was noted and also whether the residue could be removed via rinsing.
 
Static Test:
 
8) Samples were left overnight and any sediments, flocculation, separation of layers, scum on jar sides, etc. was recorded.
 
9) Samples were inverted up to 10 times and then shaken for about 10 seconds if necessary to re-mix sample.
 
10) Contents of the jars was then poured through the stacked 50 and 100 standard mesh screens similar as under 7) and the type and amount of any residue on jar and/or screen was noted and also whether the residue could be removed via rinsing.
 
Rating Scale for Compatibility:
         “Compatible”=no separation, no sediment, and no residue on jar or screen.   “Compatible with agitation”=separation or sediment re-mixed easily; screen and jar were clear after rinsing.   “Marginally compatible with agitation-sediment”=separation and/or sediment required up to 10 inversions and/or shaking to re-mix. Moderate residue remained on screen and/or jar remained. Recommendation to end user of such “marginally compatible” dilutions is that a tank clean up will be required if the tank-mixture is left to sit for an extended period of time (2-6 hours), and that the tank-mixture should not be left to sit overnight.   “Incompatible”=moderate to heavy residue remained on jar and/or screen after rinsing.       

     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Formulations 9 and 10 were diluted with commercial liquid fertilizers and  
               
               
                 then the procedure 1)-10) above was applied. The compatibility rating  
               
               
                 scale was then applied. 
               
            
           
           
               
               
               
            
               
                 Fertilizer 
                 Formulation 9 
                 Formulation 10 
               
               
                   
               
               
                 10-34-0 (commodity material,  
                 Compatible 
                 Marginally Compatible  
               
               
                 multiple manufacturers) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 2-15-19-3S (Conklin) 
                 Compatible 
                 Compatible 
               
               
                 3-18-18 (Conklin) 
                 Compatible 
                 Marginally Compatible  
               
               
                   
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 32-0-0 (commodity material,  
                 Compatible 
                 Compatible 
               
               
                 multiple manufacturers) 
                   
                   
               
               
                 4-10-10 (Pearl City Elevator) 
                 Compatible 
                 Compatible 
               
               
                 4-10-10 w/zinc 9% EDTA (Pearl  
                 Compatible 
                 Compatible 
               
               
                 City Elevator) 
                   
                   
               
               
                 4-10-10 w/zinc Triple Crown  
                 Compatible 
                 Compatible 
               
               
                 (Pearl City Elevator) 
                   
                   
               
               
                 5 parts 8-24-0, 1 part Sidekick  
                 Compatible 
                 Marginally Compatible  
               
               
                 (Conklin) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 8-16-11-2S (Conklin) 
                 Compatible 
                 Compatible 
               
               
                 8-24-0 (Conklin) 
                 Compatible 
                 Marginally Compatible  
               
               
                   
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 9-18-9 f (Conklin) 
                 Compatible 
                 Marginally Compatible  
               
               
                   
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Ascend PGR (Winfield  
                 Compatible 
                 Compatible 
               
               
                 Solutions LLC) 
                   
                   
               
               
                 Aventine (CHS Inc) 
                 Compatible 
                 Compatible 
               
               
                 Chadwick Oil and Ag 6-24-6  
                 Compatible 
                 Marginally Compatible  
               
               
                 (1/4 Zn) (Chadwick Oil and Ag  
                   
                 (Heavy residue rinsed  
               
               
                 Inc) 
                   
                 through sieves) 
               
               
                 Gavilon 120 LC 
                 Compatible 
                 Compatible 
               
               
                 Helena Nucleus O-Phos 8-24-0 
                 Compatible 
                 Compatible 
               
               
                 Helena Nucleus Ortho-Phos  
                 Compatible 
                 Marginally Compatible  
               
               
                 NPK ZN 7-21-2 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Hi-Test Complete Nutritional  
                 Compatible 
                 Marginally Compatible  
               
               
                 Starter (8-18-4) (High Test  
                   
                 (Heavy residue rinsed  
               
               
                 Labs) 
                   
                 through sieves) 
               
               
                 HyperLink (Helena Chemical  
                 Compatible 
                 Marginally Compatible  
               
               
                 Co) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Insta-Gro 3-18-18-1 (Insta-gro 
                 Compatible 
                 Marginally Compatible  
               
               
                 Manufacturing Inc) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Insta-Gro 5-20-5-1 (Insta-gro 
                 Compatible 
                 Marginally Compatible  
               
               
                 Manufacturing Inc) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Insta-Gro 9-18-9-1 (Insta-gro 
                 Compatible 
                 Marginally Compatible  
               
               
                 Manufacturing Inc) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Mixture of Nresponse (24-0-0- 
                 Compatible 
                 Compatible 
               
               
                 15), eNhance, and Pro- 
                   
                   
               
               
                 Germinator (9-24-3) (Agro- 
                   
                   
               
               
                 culture Liquid Fertilizers) 
                   
                   
               
               
                 Morral Companies 9-18-9-1S- 
                 Compatible 
                 Marginally Compatible  
               
               
                 0.1Zn (Morral Co) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Nachurs 6-24-6 + S (Nachurs  
                 Compatible 
                 Marginally Compatible  
               
               
                 Alpine Solutions) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Nachurs 9-18-9 (Nachurs Alpine 
                 Compatible 
                 Marginally Compatible  
               
               
                 Solutions) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Nachurs LKW20 (9-20-3)  
                 Compatible 
                 Marginally Compatible  
               
               
                 (Nachurs Alpine Solutions) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Nachurs Upstart (6-20-6)  
                 Compatible 
                 Marginally Compatible  
               
               
                 (Nachurs Alpine Solutions) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Nachurs W18-S (9-18-9-1)  
                 Compatible 
                 Marginally Compatible  
               
               
                 (Nachurs Alpine Solutions) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 Nutra-Flow GoldStart (6-24-6)  
                 Compatible 
                 Marginally Compatible  
               
               
                 (The Andersons) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 P Max Plus (7-20-3) (Rosen&#39;s  
                 Compatible 
                 Marginally Compatible  
               
               
                 Inc) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 PhosPlus (Biofeed Solutions  
                 Compatible 
                 Compatible 
               
               
                 Inc) 
                   
                   
               
               
                 PhosPlus + 9-15-4 (United  
                 Compatible 
                 Compatible 
               
               
                 Suppliers Inc) 
                   
                   
               
               
                 Redline (West Central Inc) 
                 Compatible 
                 Compatible 
               
               
                 RiseR 7-17-3 (Loveland  
                 Compatible 
                 Compatible 
               
               
                 Products Inc) 
                   
                   
               
               
                 Twin States Liquibrom (Twin  
                 Compatible 
                 Marginally Compatible  
               
               
                 State Inc) 
                   
                 (Heavy residue rinsed  
               
               
                   
                   
                 through sieves) 
               
               
                 X-Cell Growth Boost (Soil- 
                 Compatible 
                 Compatible 
               
               
                 Biotics) 
                   
                   
               
               
                 X-Cell MicroNutrient  
                 Compatible 
                 Compatible 
               
               
                 Supplement (Soil-Biotics) 
               
               
                   
               
            
           
         
       
     
     It has surprisingly been found that Formulation 9 is compatible with all of the major liquid fertilizers and can thus be advantageously applied in the field. 
     (d) Improved Cleanout Properties: 
     The following protocol was used to test the cleanout properties of formulation 9 in comparison with formulation 10: 
     1. The initial dry weight of individual pieces was recorded and that will be used during the testing to set a baseline for comparisons. 
     2. The formulation was applied to each material in a manner that is consistent with the actual application scenario. 
     3. The formulation allowed to sit/dry off for 7 days. 
     4. After the 7 days period, a standard cleaning process was performed for each item (different for each item used). 
     5. Coupler parts were wiped with a wet rag to clean and remove any material left from the formulation. 
     6. Filter and filter bowls were cleaned by pumping water through them at a rate of 25 oz. (708.34 grams)/min for 2 and 5 minutes. 
     7. Hose material was also cleaned by pumping 25 oz./min of fresh water through for 2 and 5 minutes. 
     8. Nozzles and caps were rinsed lightly with water. 
     9. Red Ball monitors were cleaned by pumping approximately 40 oz./min of fresh water through for 2 and 5 minutes. 
     10. After each item was rinsed/cleaned, any residue remaining was allowed to dry down and a final dry weight (for the filters, hoses and red balls repeat this for the 2 min flush and the 5 min flush) was recorded. 
     
         
         
           
             MASTERFLEX® pump was used to precisely pump desired flow rate through select materials 
           
         
       
    
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 The results for formulation 9 and 10 using the above protocol: 
               
            
           
           
               
               
               
               
            
               
                   
                   
                   
                 Residue 
               
               
                   
                 Formulation 9 
                 Formulation 10 
                 remaining (g) 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 Initial 
                 Final 
                 Initial 
                 Final 
                   
                 Formu- 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 weight 
                 weight 
                 weight 
                 weight 
                 Formu- 
                 lation 
               
               
                 Items 
                 (g) 
                 (g) 
                 (g) 
                 (g) 
                 lation 9 
                 10 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Colder 
                 30.0 
                 30.1 
                 29.2 
                 30.3 
                 0.1 
                 1.1 
               
               
                 Couplers 
               
               
                 Spray Nozzles 
                 10.6 
                 10.8 
                 10.7 
                 11.0 
                 0.2 
                 0.3 
               
               
                 Filter 
                 22.1 
                 25.3 
                 21.7 
                 39.6 
                 3.2 
                 17.9 
               
               
                 Housing + 
               
               
                 Strainer 
               
               
                 Red Ball 
                 167.7 
                 171.1 
                 167.7 
                 175.0 
                 3.4 
                 7.3 
               
               
                 Monitors 
               
               
                 Hose 
                 51.8 
                 52.4 
                 50.8 
                 55.2 
                 0.6 
                 4.7 
               
               
                   
               
            
           
         
       
     
     It was found that formulation 9 surprisingly provided much improved cleanout properties compared with the current commercial aqueous capsule suspension (formulation 10).