Siloxane nonionic blends useful in agriculture

Abstract: Disclosed are compositions of nonionic siloxane alkoxylates with aminopolyalkyleneoxide surfactants which are useful in treating plants, for instance as adjuvants for pesticides including in particular herbicides. These compositions overcome the antagonism associated with nonionic trisiloxane alkoxylates on pesticide uptake in plants.

Description: Many pesticides require the addition of an adjuvant to the spray mixture to provide wetting and spreading on foliar surfaces. Often that adjuvant is a surfactant which can perform a variety of functions, such as increasing spray droplet retention on difficult to wet leaf surfaces, or to provide penetration of the herbicide into the plant cuticle. These adjuvants are either provided as a component in an adjuvant formulation or used as an additive in herbicide formulations. Trisiloxane alkoxylates are well known for their ability to provide enhanced spreading and wetting properties to pesticide spray solutions, relative to more commonly used organic based (nonsilicone) surfactants. At times it is necessary to include other surfactants in the spray mixture along with the trisiloxane alkoxylate. Unfortunately, the presence of many classes of cosurfactants interfere with the performance of the trisiloxane alkoxylate. PCT Publication No. WO 89 12394 by Monsanto discloses herbicidal compositions with an organosilicone surfactant, such as SILWET® L-77, and many classes of cosurfactants. However, when rainfall does not occur, the SILWET® L-77 is antagonistic to an herbicide such as glyphosate regardless of the cosurfactants used. Thus, the Monsanto focus is on finding particular silicone surfactants which are not antagonistic to glyphosate. There is no teaching of any cosurfactants that would reduce antagonism towards the trisiloxane alkoxylate. The present invention teaches a surfactant composition of nonionic siloxane alkoxylates and aminoalkyleneoxide surfactant, and their use as adjuvants, for pesticides. The present invention provides a surfactant composition that gives enhanced wetting of spray solutions on difficult to wet surfaces, such as waxy plants, and enhance the uptake of agrichemicals into plants as compared to more commonly used blends of polyalkyleneoxide/trisiloxane alkoxylate surfactants. The composition of the present invention is useful as a tank side additive, or as a component in a herbicide formulation. In addition, the compositions of the present invention are useful as adjuvants for other pesticides, such as fungicides, insecticides, plant growth regulators, acaracides and the like. More specifically, the present invention is directed to a composition comprising (a) a nonionic siloxane of the formula: R 5 Me 2 SiO[Me 2 SiO] f [MeSi(Q)O] g SiMe 2 R 5 wherein f=0 to 1, g=1 to 2, Q=C d H 2d O(C 2 H 4 O) t (C 3 H 6 O) w R 4 , d=2 to 4, t=3 to 12, w=0 to 8, R 4 is hydrogen, acetyl or a hydrocarbon radical containing 1 to 4 carbon atoms, and R 5 is Q, alkyl of one to four carbons or a hydroxyl group; and (b) an aminopolyalkyleneoxide of the formula (H(R T ) T ) 2 NC 2 H 4 N((R T ) T H) 2 wherein R T denotes alkoxy groups containing 2 or 3 carbon atoms each, and the subscript T is selected so that the molecular weight of the alkoxylated diamine is 1,000 to 15,000. The present invention provides novel surfactant compositions that are useful as adjuvants for pesticides. The compositions of the present invention provide enhanced spray coverage relative to conventional wetting agents. In addition, these products provide a low aqueous surface tension (<23 mN/m at 0.1 wt%), which is necessary and desirable for spreading of pesticide solutions. COMPOSITION The compositions of the present invention include a nonionic siloxane alkoxylate and an aminopolyalkyleneoxide. a. Nonionic siloxane alkoxylate The siloxane alkoxylate has the general formula: R 5 Me 2 SiO[Me 2 SiO] f [MeSi(Q)O] g SiMe 2 R 5 wherein f=0 to 1, preferably 0, g=1 to 2, preferably 1, Q=C d H 2d O(C 2 H 4 O) t (C 3 H 6 O) w R 4 , d=2 to 4, preferably 3, t=3 to 12, preferably 4 to 8, w=0 to 8, providing that when w is greater than 0, (t+w) is preferably between 5 and 12. R 4 is hydrogen, acetyl or hydrocarbon radical containing between 1 and 4 carbon atoms. R 5 is Q, alkyl of 1 to 4 carbon atoms or a hydroxyl group. The preferred nonionic siloxane alkoxylates are trisiloxane alkoxylates, which have f=0, g=1, d=3, t=4 to 8, w=0, R 4 is H or Me. b. Aminopolyalkyleneoxide The compositions of the present invention also contain aminopolyalkyleneoxide surfactants which do not detract from the efficacy of the composition. Examples include alkoxylated diamines of the formula [H(OH 2a C a ) T ] 2 -NC 2 H 4 N-[(C a H 2a O) T H] 2 wherein a is 2 or 3 denoting the alkoxy groups, and T is selected so that the molecular weight of the alkoxylated diamine is 1000 to 15,000. Preferably, ethoxy units comprise 10 to 90% and more preferably 20 to 50% of the polyalkoxylate chains. The ratio of the aminopolyalkyleneoxide to the nonionic siloxane alkoxylate is in the range of 99:1 and 1:99 by weight. The compositions of the present invention also optionally include ingredients for use herein which are pesticides, especially acid functional ones, e.g., compounds that contain at least one carboxylic, sulfonic or phosphonic acid group which is in the form of the free acid or a salt or ester thereof. The term pesticide means any compound used to destroy pests, e.g., insecticides, rodenticides, fungicides, and herbicides, and is also used herein to include plant herbicides, and is also used herein to include plant growth regulatory compounds. Illustrative examples of pesticides which can be employed include, but are not limited to, growth regulators, photosynthesis inhibitors, pigment inhibitors, mitotic disrupters, lipid biosynthesis inhibitors, cell wall inhibitors, and cell membrane disrupters. The amount of pesticide employed in compositions of the invention varies with the type of pesticide employed. More specific examples of pesticide compounds that can be used with the compositions of the invention are: phenoxy acetic acids, phenoxy propionic acids, phenoxy butyric acids, benzoic acids, triazines and s-triazines, substituted ureas, uracils, bentazon, desmedipham, methazole, phenmedipham, pyridate, amitrole, clomazone, fluridone, norflurazone, dinitroanilines, isopropalin, oryzalin, pendimethalin, prodiamine, trifluralin, glyphosate, glufosinate, sulfonylureas, imidazolinones, clethodim, diclofop-methyl, fenoxaprop-ethyl, fluazifop-P-butyl, haloxyfop-methyl, quizalofop, sethoxydim, cyclohexanediones, aryloxyphenoxypropanoates, dichlobenil, isoxaben, and bipyridylium compounds. MANUFACTURE The nonionic siloxane alkoxylates, aminoalkyleneoxide surfactants, and pesticides are commercially available and their manufacture is known in the art. USE The nonionic siloxane alkoxylates, aminoalkyleneoxide surfactant blends of the present invention, primarily are intended for use in the agricultural field as adjuvants for pesticide, especially acid functional pesticides, containing aqueous end-use formulations. The compositions of the present invention are added directly to a spray tank along with an acid functional pesticide, or as part of a pesticide formulation. They are used in an effective amount, that is, an amount which is sufficient to cause the pesticide to function effectively in the formulation. When used as a tankside additive, the compositions of this invention should be present at weight concentrations between 0.01% and 5.0%, preferably between 0.025% and 0.5%, but in "in can" formulations, the compositions of the present invention may be present at concentrations that will deliver between 0.01% and 5.0% to the final use dilution, preferably between 0.025% and 0.5%, of the final use dilution. The novel nonionic siloxane alkoxylates/aminoalkyleneoxide surfactant compositions of the present invention may also be used generally as surface active agents in aqueous formulation where there is an acid functionalized component, including, but not limited to, surfactants, wetting agents and softeners for textiles, as flowing and leveling agents in coatings, in hair care products and creams for personal care applications and as anti-static agents and softeners for laundry products. Other uses for the present composition will be obvious to those of skill in the art. EXAMPLES The following examples are presented to further illustrate and explain the present invention and should not be taken as limiting in any regard. Unless otherwise indicated, all parts and percentages are by weight, and are based on the weight at the particular stage of the processing being described. Example 1 The composition of the present invention contains at least one surfactant from the class of nonionic siloxane alkoxylates (a), and at least one surfactant from the class of aminoalkyleneoxide surfactants (b). a. Nonionic Siloxane Alkoxylates: Tables 1 and 2 describe the trisiloxane alkoxylates used herein as illustrative examples of the compositions of the present invention. They have the following structure: (CH 3 ) 3 Si-O-Si(CH 3 )(Q)-O-Si(CH 3 ) 3 Reference Nominal Formula of the Q Group TSA-1 C 3 H 6 O(C 2 H 4 O) 8 CH 3 , SILWET L-77® Surfactant TSA-2 C 3 H 6 O(C 2 H 4 O) 8 OH, SILWET® 408 b. Aminoalkyleneoxide Surfactants Table 2 provides structural information on the aminoalkyleneoxide surfactants component of this instant invention. The aminopolyalkyleneoxide surfactants may be blocked, or random alkyleneoxide groups. The examples of the aminoalkyleneoxides of Table 2 are represented by the formula: [H(OH 2a C a ) T ] 2 -NC 2 H 4 N-[(C a H 2a O) T H] 2 wherein a and T are as previously defined. The wt.% EO and wt.% PO correlate to the percentage of ethylene oxide units and propylene oxide units, respectively, contained in the alkyleneoxide group that repeat T times to give a compound of the specified molecular weight. Description of Conventional Aminoalkyleneoxide Surfactants References MW Wt.%EO Wt.%PO Configuration of EO/PO AAO-1 1,650 40 - 60 Terminal EO block AAO-2 3,600 10 90 Terminal EO block AAO-3 5,500 40 60 Terminal EO block AAO-4 6,700 40 60 Terminal EO block AAO-5 25,000 80 20 Terminal EO block AAO-6 30,00 80 20 Terminal EO block Comparative Nonsilicone Surfactants: Table 3 provides descriptions of a typical comparative, nonsilicone surfactant used as an agricultural wetting agent. Description of Comparative Conventional Nonsilicone Surfactant Ref. MW Wt%EO Remarks PAO-A 2150 20 PLURONIC® 17R2 (BASF Corp.), polyalkyleneoxide block copolymer surfactant (PO-EO-PO type). PAO-B 2500 20 PLURONIC® L-62 (BASF Corp.), polyalkyleneoxide block copolymer surfactant (EO-PO-EO type). OPE NA 10 TRITON® X-100 (Union Carbide Corp.) Octylphenol ethoxylate TAE NA 5 ETHOMEEN® T/15 (Akzo Nobel Corp.) Tallow amine ethoxylate Example 2 - Spreading This example demonstrates that the surfactant blend compositions of the present invention are favorable in their ability to provide spreading properties equivalent to the commonly used PAO-A/TSA-1 blends. Table 4 shows that although the aminoalkyleneoxide surfactants are a unique class of surfactants, these materials do not inhibit the spreading properties of the TSA-1, when compared at equivalent TSA-1 concentrations (compare ID 29 to 31 with AAO/TSA-1 blends). Additionally, TSA-1 blends, with either OPE or TAE, show a significant reduction in the spreading properties as compared to the compositions of the present invention (compare ID 32 and 33 with AAO/TSA-1 blends). Spreading was determined by applying a 10µL droplet of surfactant solution to a polyester film (3M, Write-On film) and measuring the spread diameter after 30 seconds. The solution was applied with an automatic pipette to provide droplets of reproducible volume. Deionized water that was further purified with a Millipore filtration system was used to prepare the surfactant solutions. Comparison of Spreading Properties (@0.1 wt%) of TSA-1/Cosurfactant Blends ID Cosurfactant Composition of Invention Wt% TSA-1 Wt% Cosurfactant Spread Diameter (mm) 1 AAO-1 No 0 0.1 6 2 AAO-1 Yes 0.025 0.075 22 3 AAO-1 Yes 0.05 0.05 29 4 AAO-1 Yes 0.075 0.025 39 5 AAO-2 No 0 0.1 7 6 AAO-2 Yes 0.025 0.075 19 7 AAO-2 Yes 0.05 0.05 36 8 AAO-2 Yes 0.075 0.025 43 9 AAO-4 No 0 0.1 6 10 AAO-4 Yes 0.025 0.075 24 11 AAO-4 Yes 0.05 0.05 35 12 AAO-4 Yes 0.075 0.025 44 13 AAO-5 No 0 0.1 6 14 AAO-5 Yes 0.025 0.075 21 15 AAO-5 Yes 0.05 0.05 35 16 AAO-5 Yes 0.075 0.025 45 17 AAO-6 No 0 0.1 7 18 AAO-6 Yes 0.025 0.075 22 19 AAO-6 Yes 0.05 0.05 35 20 AAO-6 Yes 0.075 0.025 43 25 PAO-A No 0 0.1 7 26 PAO-A No 0.025 0.075 27 27 PAO-A No 0.05 0.05 35 28 PAO-A No 0.075 0.025 45 29 None N/A 0.025 0 20 30 None N/A 0.050 0 31 31 None N/A 0.075 0 40 32 OPE No 0.05 0.05 20 33 TAE No 0.05 0.05 8 34 None N/A 0 0 4 Example 3 The effect of adjuvant on glyphosate efficacy was determined using a barley regrowth assay. Glyphosate treatments, with and without adjuvant, were sprayed on barley (14-16 cm tall) at rates of 0.014, 0.028 and 0.056 g acid equivalent/m 2 (0.125, 0.25 and 0.5 lbs. acid equivalent per acre (lb.ae/A)). Six hours after application, all plants were trimmed to 2 cm in height, removing 95% of the treated area. Regrowth was assessed 1 week after treatment by measuring fresh weight and plant height. The data are reported as percent inhibition as compared to the untreated control. Table 5 demonstrates that overall the compositions of the present invention (AAO/TSA-2 combinations) provide enhanced glyphosate efficacy relative to the PAO-B/TSA-2 blend, or as compared to glyphosate without surfactant as shown by higher growth inhibition rates in the fresh weight of the plants treated at the higher glyphosate levels common to commercial usage. Summary of Surfactant Effects on Glyphosate Activity ID Surfactant Composition of Invention Glyphosate g.ae/m 2 (lb. ae/A) % Inhibition Fresh Wt.% 22 AAO-1/TSA-2 Yes 0.056 (0.5) 57.2 23 AAO-2/TSA-2 Yes 0.028 (0.25) 23.2 24 AAO-1/TSA-2 Yes 0.02 (0.175) 14.4 32 AAO-2/TSA-2 Yes 0.056 (0.5) 70.3 33 AAO-2/TSA-2 Yes 0.028 (0.25) 52.5 34 AAO-2/TSA-2 Yes 0.02 (0.175) 2.6 35 AAO-3/TSA-2 Yes 0.056 (0.5) 72.5 36 AAO-3/TSA-2 Yes 0.028 (0.25) 25.2 37 AAO-3/TSA-2 Yes 0.02 (0.175) 12.2 41 PAO-B/TSA-2 No 0.056 (0.5) 49.8 42 PAO-B/TSA-2 No 0.028 (0.25) 43.8 43 PAO-B/TSA-2 No 0.014 (0.125) 21.4 44 None N/A 0.056 (0.5) 39.7 45 None N/A 0.028 (0.25) 20.2 46 None N/A 0.014 (0.125) 0.6

Claims: A composition comprising a. a nonionic siloxane of the formula: R 5 Me 2 SiO[Me 2 SiO] f [MeSi(Q)O] g SiMe 2 R 5 wherein f=0 to 1, g=1 to 2, Q=C d H 2d O(C 2 H 4 O) t (C 3 H 6 O) w R 4 , d=2 to 4, t=3 to 12, w=0 to 8, R 4 is hydrogen, acetyl or a hydrocarbon radical containing between 1 and 4 carbon atoms, and R 5 is Q, alkyl of 1 to 4 carbon atoms or a hydroxyl group; and b. an aminopolyalkyleneoxide of the formula [H(OH 2a C a ) T ] 2 -NC 2 H 4 N-[(C a H 2a O) T H] 2 wherein a is 2 or 3, and T is selected so that a molecular weight of the alkoxylated diamine is 1,000 to 15,000. A composition according to claim 1 wherein a weight ratio of component a. to component b. is 1:99 to 99:1. A composition according to claim 1 additionally comprising an acid functional pesticide. A composition according to claim 3 wherein the acid functional pesticide is selected from the group consisting of: growth regulators, photosynthesis inhibitors, pigment inhibitors, mitotic disrupters, lipid biosynthesis inhibitors, cell wall inhibitors, and cell membrane disrupters. A composition according to claim 3 wherein the pesticide is a herbicide selected from the group consisting of: phenoxy acetic acids, phenoxy propionic acids, phenoxy butyric acids, benzoic acids, triazines and s-triazines, substituted ureas, uracils, bentazon, desmedipham, methazole, phenmedipham, pyridate, amitrole, clomazone, fluridone, norflurazone, dinitroanilines, isopropalin, oryzalin, pendimethalin, prodiamine, trifluralin, glyphosate, glufosinate, sulfonylureas, imidazolinones, clethodim, diclofop-methyl, fenoxaprop-ethyl, fluazifop-P-butyl, haloxyfop-methyl, quizalofop, sethoxydim, dichlobenil, isoxaben, and bipyridylium compounds. A process for treating plants comprising applying to plants an effective amount of a composition according to claim 1. A process for treating plants comprising applying to plants an effective amount of a composition according to claim 2. A process for treating plants comprising applying to plants an effective amount of a composition according to claim 3. A process for treating plants comprising applying to plants an effective amount of a composition according to claim 4. A process for treating plants comprising applying to plants an effective amount of a composition according to claim 5.

Inventors: POLICELLO GEORGE, STEVENS PETER, POLICELLO, GEORGE, STEVENS, PETER
Applicants: CROMPTON CORP, CROMPTON CORPORATION
Application year: 1998
Main classification: A01N25
IPC codes: B01F17, A01N25, A01N57