Abstract:
The present invention provides agricultural surfactant adjuvants that enhance the bioefficacy of herbicides and other pesticides. Also provided are agriculturally-valuable compositions containing such surfactant adjuvants. One advantage to an adjuvant composition according to the invention is combined high efficacy and low toxicity, including low eye and skin irritancy and low aquatic toxicity. Sequesterant agents can also be added to condition calcium or other interfering ions or species present in spray water.

Description:
FIELD OF THE INVENTION  
         [0001]    The present invention relates to agricultural adjuvants, and, more particularly, to surfactant adjuvants that enhance the bioefficacy of herbicides and other pesticides. The invention also relates to agriculturally-valuable compositions containing such surfactant adjuvants.  
         DESCRIPTION OF THE RELATED ART  
         [0002]    N-phosphonomethylglycine and its herbicidally-active salts, including those as described in U.S. Pat. No. 3,799,758 and EP-A-0088180 (hereinafter collectively referred to as “glyphosate”) have become important herbicides. It is known in the art that glyphosate can be made more efficacious with the use of surfactant adjuvants. U.S. Pat. No. 5,668,085 discloses the use of alkoxylated alkyl amine surfactants in glyphosate herbicidal compositions. The use of alkyl amine ethoxylate surfactants with glyphosate has been published by Wyrill and Burnside, Weed Science Vol. 25 (1977), 275-287. This class of surfactants has found widespread use in glyphosate formulations.  
           [0003]    U.S. Pat. No. 5,750,468. discloses the use of ether amine alkoxylate surfactants in glyphosate herbicidal formulations. While the adjuvant surfactant chemistries disclosed in these two patents provide highly efficient weed control, their toxicity profiles leave room for improvement.  
           [0004]    One method of reducing the eye irritation of polyoxyalkylene alkylamine surfactants is disclosed in U.S. Pat. No. 5,683,985 in which it is taught that an alkylamine adjuvant is combined with an effective amount of an additional acidic surfactant to provide a formulation that causes a reduced level of eye irritation. However, no specific contribution to herbicidal activity is claimed for this anionic surfactant by itself, only reduced eye irritation. Further, no mention is made for this adjuvant composition relating to the degree of aquatic toxicity it possesses. Thus, the prior art as failed thus far in providing adjuvant compositions which possess low levels of eye irritation and aquatic toxicity, while providing enhanced efficacy for pesticides, such as glyphosate.  
           [0005]    The foregoing patents and patent publications mentioned herein are all incorporated by reference thereto.  
         BRIEF SUMMARY OF THE INVENTION  
         [0006]    The present invention is directed to an adjuvant composition for use in pesticide formulations. An adjuvant composition according to the invention is highly efficacious, has low eye and skin irritancy, and low aquatic toxicity. In addition, other chemical components normally used by formulators in the pesticide arts can be included in a final product which utilizes an adjuvant composition according to the invention. These include without limitation hydrotropes, or sequestering compounds which effectively mask the presence of calcium and other ionic species frequently regarded as detrimental In one form of the present invention there is provided an adjuvant comprising a mixture of a polyalkoxylated alkylamine surfactant in combination with a polyalkoxylated alkyldiamine surfactant. This composition combines two surfactants which individually have been shown to be efficacious in glyphosate formulations, and exhibit synergy when applied together.  
           [0007]    A composition according to the invention also is user-friendly, as shown by both low eye irritancy and low skin irritancy. In addition, the herbicidal formulation containing an adjuvant composition according to the invention also possesses low aquatic toxicity. This key feature is important when herbicidal formulations are applied in locations where runoff to local streams and watersheds occurs.  
           [0008]    The addition of a chemical such as EDTA, citric acid, or ammonium sulfate can eliminate or reduce the adverse effects of calcium on the efficacy of glyphosate herbicides.  
           [0009]    Thus, one aspect of the present invention is an adjuvant composition comprising:  
           [0010]    a) a polyoxyalkylene alkylamine of the formula:  
                         
 
           [0011]    in which x is any whole integer between 5 and 21; R 1  and R 2  may independently be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight chain or branched; y, z, p, and q are each independently selected from any whole integer between 0 and 60, including 0 and 60, and subject to the provisos that at least one of y and p is greater than 0, and at least one of z and q is greater than zero, wherein the alkoxy moieties may be conformed in either a random, block, or multiple block fashion; and  
           [0012]    b) a polyoxyalkylene alkyldiamine of the formula:  
                         
 
           [0013]    in which p is any integer selected from 1, 2, 3, 4, 5, and 6; and each of R1, R2, R3, and R4 are independently selected from the group consisting of: H, and an alkoxy moiety selected from either:  
           —(R 1 O) x H; or   i  
           —(R 1 O) x (R 2 O) y H   ii  
           [0014]    in which R 1  and R 2  may each be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; wherein x and y may each independently be any number between 1 and 150, subject to the proviso that the sum of x+y is in the range of 1 to 200; and wherein when the alkoxy moiety is —(R 1 O) x (R 2 O) y —, such alkoxy moiety may be conformed either a random, block, or multiple block fashion.  
           [0015]    Another aspect of the present invention is an adjuvant composition comprising:  
           [0016]    a) a polyoxyalkylene alkylamine of the formula:  
                         
 
           [0017]    in which x is any whole integer between 5 and 21; R 1  and R 2  may independently be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight chain or branched; y, z, p, and q are each independently selected from any whole integer between 0 and 60, including 0 and 60, and subject to the provisos that at least one of y and p is greater than 0, and at least one of z and q is greater than zero, wherein the alkoxy moieties may be conformed in either a random, block, or multiple block fashion; and  
           [0018]    b) a polyoxyalkylene polyalkylpolyamine of the formula:  
                         
 
           [0019]    in which R 1  and R 2  are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or a radical of the formula:  
                         
 
           [0020]    in which R 3  in each occurrence may be an alkyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6, straight-chain or branched; R 4  in each occurrence is a straight-chain or branched alkyl bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; Z is a hydroxy group or alkyl group containing 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; q is any integer between 0 and 400; and wherein X is any of:  
           [0021]    i) a hydroxy group or an alkyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6; or  
           [0022]    ii) a group  
                         
 
           [0023]    in which R 5  and R6 are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or  
                         
 
           [0024]    as defined above in which Z is a hydroxy group or an alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms, and in which R 7  is a straight-chain or branched alkylene bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; or  
           [0025]    iii) a moiety of the formula:  
                         
 
           [0026]    in which R 10 , R 11 , R 14 , and R 15  are each independently selected from the group of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; the moiety  
                         
 
           [0027]    as defined above in which Z is a hydroxy or alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms; R 8  and R 12  are each independently alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; R 9 , R 13 , and R 21  are each independently selected from a straight-chain or branched alkyl bridging linkage having 1, 2, 3, 4, 5, or 6 carbon atoms; R 16 , R 17 , R 18 , R 19 , R 20  are each independently selected from hydrogen or an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms; d is 0 or 1; a is any integer between 0 and 100, with the proviso that when X is a moiety of the formula given in iii) above, b and c may each independently be any integer in the range of 0 to 390, and the sum of a+b+c is any number between 2 and 400.  
           [0028]    Another aspect of the invention provides an adjuvant composition comprising:  
           [0029]    a) a compound having the formula:  
                         
 
           [0030]    in which x is any whole integer between 1 and 21; R 1 , R 2 , and R 3  may independently be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight chain or branched; R 4  is any alkyl group having any number of carbon atoms between 5 and 23, whether straight-chain or branched; y, z, p, and q are each independently selected from any whole integer between 0 and 60, including 0 and 60, and subject to the provisos that at least one of y and p is greater than 0, and at least one of z and q is greater than zero, wherein the alkoxy moieties may be conformed in either a random, block, or multiple block fashion; and  
           [0031]    b) a polyoxyalkylene alkyldiamine of the formula:  
                         
 
           [0032]    in which p is any integer selected from 1, 2, 3, 4, 5, and 6; and each of R1, R2, R3, and R4 are independently selected from the group consisting of: H, and an alkoxy moiety selected from either:  
           —(R 1 O) x H; or   i  
           —(R 1 O) x (R 2 O) y H   ii  
           [0033]    in which R 1  and R 2  may each be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; wherein x and y may each independently be any number between 1 and 150, subject to the proviso that the sum of x+y is in the range of 1 to 200; and wherein when the alkoxy moiety is —(R 1 O) x (R 2 O) y —, such alkoxy moiety may be conformed either a random, block, or multiple block fashion.  
           [0034]    Yet another aspect of the invention provides an adjuvant composition comprising:  
           [0035]    a) a compound of the formula:  
                         
 
           [0036]    in which x is any whole integer between 1 and 21; R 1 , R 2 , and R 3  may independently be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight chain or branched; R 4  is any alkyl group having any number of carbon atoms between 5 and 23, whether straight-chain or branched; y, z, p, and q are each independently selected from any whole integer between 0 and 60, including 0 and 60, and subject to the provisos that at least one of y and p is greater than 0, and at least one of z and q is greater than zero, wherein the alkoxy moieties may be conformed in either a random, block, or multiple block fashion; and  
           [0037]    b) a polyoxyalkylene polyalkylpolyamine of the formula:  
                         
 
           [0038]    in which R 1  and R 2  are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or a radical of the formula:  
                         
 
           [0039]    in which R 3  in each occurrence may be an alkyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6, straight-chain or branched; R 4  in each occurrence is a straight-chain or branched alkyl bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; Z is a hydroxy group or alkyl group containing 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; q is any integer between 0 and 400; and wherein X is any of:  
           [0040]    i) a hydroxy group or an alkyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6; or  
           [0041]    ii) a group  
                         
 
           [0042]    in which R 5  and R6 are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or  
                         
 
           [0043]    as defined above in which Z is a hydroxy group or an alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms, and in which R 7  is a straight-chain or branched alkylene bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; or  
           [0044]    iii) a moiety of the formula:  
                         
 
           [0045]    in which R 10 , R 11 , R 14 , and R 15  are each independently selected from the group of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; the moiety  
                         
 
           [0046]    as defined above in which Z is a hydroxy or alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms; R 8  and R 12  are each independently alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; R 9 , R 13 , and R 21  are each independently selected from a straight-chain or branched alkyl bridging linkage having 1, 2, 3, 4, 5, or 6 carbon atoms; R 16 , R 17 , R 18 , R 19 , R 20  are each independently selected from hydrogen or an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms; d is 0 or 1; a is any integer between 0 and 100, with the proviso that when X is a moiety of the formula given in iii) above, b and c may each independently be any integer in the range of 0 to 390, and the sum of a+b+c is any number between 2 and 400.  
           [0047]    Yet another aspect of the invention provides an adjuvant composition comprising:  
           [0048]    a) a compound having the formula:  
                         
 
           [0049]    in which R 1 , and R 4  are each independently any alkyl group having any number of carbon atoms between 5 and 23, whether straight chain or branched; R 2 , R 3 , R 5 , R 6 , R 7 , and R 8  of the alkoxy groups may independently be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight chain or branched; a, b, c, and d are each independently selected from any whole integer between 0 and 15, including 0 and 15, and subject to the provisos that at least one of a and b is greater than 0, and at least one of c and d is greater than zero; e and f are independently selected from any whole integer between 0 and 150, with the sum of e and f being any integer between 0 and 150, subject to the proviso that at least one of e and f is greater than zero; and wherein the alkoxy moieties may be conformed in either a random, block, or multiple block fashion; and  
           [0050]    b) a polyoxyalkylene alkyldiamine of the formula:  
                         
 
           [0051]    in which p is any integer selected from 1, 2, 3, 4, 5, and 6; and each of R1, R2, R3, and R4 are independently selected from the group consisting of: H, or an alkoxy moiety selected from either:  
           —(R 1 O) x H; or   i  
           —(R 1 O) x (R 2 O) y H   ii  
           [0052]    in which R 1  and R 2  may each be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; wherein x and y may each independently be any number between 1 and 150, subject to the proviso that the sum of x+y is in the range of 1 to 200; and wherein when the alkoxy moiety is —(R 1 O) x (R 2 O) y —, such alkoxy moiety may be conformed either a random, block, or multiple block fashion.  
           [0053]    Yet another aspect of the invention provides an adjuvant composition comprising:  
           [0054]    a) a compound having the formula:  
                         
 
           [0055]    in which R 1  and R 4  are each independently any alkyl group having any number of carbon atoms between 5 and 23, whether straight chain or branched; R 2 , R 3 , R 5 , R 6 , R 7  and R 8  of the alkoxy groups may independently be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight chain or branched; a, b, c, and d are each independently selected from any whole integer between 0 and 15, including 0 and 15, and subject to the provisos that at least one of a and b is greater than 0, and at least one of c and d is greater than zero; e and f are independently selected from any whole integer between 0 and 150, with the sum of e and f being any integer between 0 and 150, subject to the proviso that at least one of e and f is greater than zero; and wherein the alkoxy moieties may be conformed in either a random, block, or multiple block fashion; and  
           [0056]    b) a polyoxyalkylene polyalkylpolyamine of the formula:  
                         
 
           [0057]    in which R 1  and R 2  are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or a radical of the formula:  
                         
 
           [0058]    in which R 3  in each occurrence may be an alkyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6, straight-chain or branched; R 4  in each occurrence is a straight-chain or branched alkyl bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; Z is a hydroxy group or alkyl group containing 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; q is any integer between 0 and 400; and wherein X is any of:  
           [0059]    i) a hydroxy group or an alkyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6; or  
           [0060]    ii) a group  
                         
 
           [0061]    in which R 5  and R 6  are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or  
                         
 
           [0062]    as defined above in which Z is a hydroxy group or an alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms, and in which R 7  is a straight-chain or branched alkylene bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; or  
           [0063]    iii) a moiety of the formula:  
                         
 
           [0064]    in which R 10 , R 11 , R 14 , and R 15  are each independently selected from the group of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; the moiety  
                         
 
           [0065]    as defined above in which Z is a hydroxy or alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms; R 8  and R 12  are each independently alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; R 9 , R 13 , and R 21  are each independently selected from a straight-chain or branched alkyl bridging linkage having 1, 2, 3, 4, 5, or 6 carbon atoms; R 16 , R 17 , R 18 , R 19 , R 20  are each independently selected from hydrogen or an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms; d is 0 or 1; a is any integer between 0 and 100, with the proviso that when X is a moiety of the formula given in iii) above, b and c may each independently be any integer in the range of 0 to 390, and the sum of a+b+c is any number between 2 and 400.  
           [0066]    Another aspect still of the present invention provides an adjuvant composition comprising:  
           [0067]    a) a polyoxyalkylene dialkylamine having the formula;  
                         
 
           [0068]    in which x and y are each independently any number between 5 and 21, thus defining straight-chain or branched alkyl groups, and wherein a and b are independently any integer between 0 and 61 and wherein the sum of a +b is any integer between 2 and 60; R 1  and R 2  may be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched and each of the groups R 1 O and R 2 O may be arranged in either a random, block, or multiple block configuration; and  
           [0069]    b) a polyoxyalkylene polyalkylpolyamine of the formula:  
                         
 
           [0070]    in which R 1  and R 2  are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or a radical of the formula:  
                         
 
           [0071]    in which R 3  in each occurrence may be an alkyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6, straight-chain or branched; R 4  in each occurrence is a straight-chain or branched alkyl bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; Z is a hydroxy group or alkyl group containing 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; q is any integer between 0 and 400; and wherein X is any of:  
           [0072]    i) a hydroxy group or an alkyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6; or  
           [0073]    ii) a group  
                         
 
           [0074]    in which R 5  and R 6  are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or  
                         
 
           [0075]    as defined above in which Z is a hydroxy group or an alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms, and in which R 7  is a straight-chain or branched alkylene bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; or  
           [0076]    iii) a moiety of the formula:  
                         
 
           [0077]    in which R 10 , R 11 , R 14 , and R 15  are each independently selected from the group of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; the moiety  
                         
 
           [0078]    as defined above in which Z is a hydroxy or alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms; R 8  and R 12  are each independently alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; R 9 , R 13 , and R 21  are each independently selected from a straight-chain or branched alkyl bridging linkage having 1, 2, 3, 4, 5, or 6 carbon atoms; R 16 , R 17 , R 18 , R 19 , R 20  are each independently selected from hydrogen or an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms; d is 0 or 1; a is any integer between 0 and 100, with the proviso that when X is a moiety of the formula given in iii) above, b and c may each independently be any integer in the range of 0 to 390, and the sum of a+b+c is any number between 2 and 400.  
           [0079]    Another aspect of the present invention provides an adjuvant composition comprising:  
           [0080]    a) a polyoxyalkylene dialkylamine having the formula;  
                         
 
           [0081]    in which x and y are each independently any number between 5 and 21, thus defining straight-chain or branched alkyl groups, and wherein a and b are independently any integer between 0 and 61, and wherein the sum of a+b is any integer between 2 and 60; R 1  and R 2  may be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched and each of the groups R 1 O and R 2 O may be arranged in either a random, block, or multiple block configuration; and  
           [0082]    b) a polyoxyalkylene alkdiamine of the formula:  
                         
 
           [0083]    in which p is any integer selected from 1, 2, 3, 4, 5, and 6; and each of R1, R2, R3, and R4 are independently selected from the group consisting of: H, or an alkoxy moiety selected from either:  
           —(R 1 O) x H; or   i  
           —(R 1 O) x (R 2 O) y H   ii  
           [0084]    in which R 1  and R 2  may each be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; wherein x and y may each independently be any number between 1 and 150 subject to the proviso that the sum of x+y is in the range of 1 to 200; and wherein when the alkoxy moiety is —(R 1 O) x (R 2 O) y —, such alkoxy moiety may be conformed either a random, block, or multiple block fashion.  
           [0085]    Another aspect of the present invention provides an adjuvant composition comprising:  
           [0086]    a) a polyoxyalkylene alkyldiamine of the formula:  
                         
 
           [0087]    in which p is any integer selected from 1, 2, 3, 4, 5, and 6; and each of R 1 , R 2 , R 3 , and R 4  are independently selected from the group consisting of: H, or an alkoxy moiety selected from either:  
           —(R 1 O) x H; or   i  
           —(R 1 O) x (R 2 O) y H   ii  
           [0088]    in which R 1  and R 2  may each be any alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; wherein x and y may each independently be any number between 1 and 150, subject to the proviso that the sum of x+y is in the range of 1 to 200; and wherein when the alkoxy moiety is —(R 1 O) x (R 2 O) y —, such alkoxy moiety may be conformed either a random, block, or multiple block fashion.  
           [0089]    b) a polyoxyalkylene polyalkylpolyamine of the formula:  
                         
 
           [0090]    in which R 1  and R 2  are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or a radical of the formula:  
                         
 
           [0091]    in which R 3  in each occurrence may be an alkyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6, straight-chain or branched; R 4  in each occurrence is a straight-chain or branched alkyl bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; Z is a hydroxy group or alkyl group containing 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; q is any integer between 0 and 400; and wherein X is any of:  
           [0092]    i) a hydroxy group or an allyl group having any number of carbon atoms selected from 1, 2, 3, 4, 5, or 6; or  
           [0093]    ii) a group  
                         
 
           [0094]    in which R 5  and R6 are each independently selected from the group consisting of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, whether straight-chain or branched; or  
                         
 
           [0095]    as defined above in which Z is a hydroxy group or an alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms, and in which R 7  is a straight-chain or branched alkylene bridging group having 1, 2, 3, 4, 5, or 6 carbon atoms; or  
           [0096]    iii) a moiety of the formula:  
                         
 
           [0097]    in which R 10 , R 11 , R 14 , and R 15  are each independently selected from the group of: hydrogen; an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; the moiety  
                         
 
           [0098]    as defined above in which Z is a hydroxy or alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms; R 8  and R 12  are each independently alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms, straight-chain or branched; R 9 , R 13 , and R 21  are each independently selected from a straight-chain or branched alkyl bridging linkage having 1, 2, 3, 4, 5, or 6 carbon atoms; R 16 , R 17 , R 18 , R 19 , R 20  are each independently selected from hydrogen or an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms; d is 0 or 1; a is any integer between 0 and 100, with the proviso that when X is a moiety of the formula given in iii) above, b and c may each independently be any integer in the range of 0 to 390, and the sum of a+b+c is any number between 2 and 400.  
           [0099]    The present invention provides pesticidal compositions comprising the foregoing adjuvants in combination with an effective amount of a pesticide.  
           [0100]    The present invention further provides pesticidal compositions comprising the foregoing adjuvants, combined with an effective amount of a pesticide, in further combination with a chelating agent.  
           [0101]    The present invention further provides pesticidal compositions comprising the foregoing adjuvants, combined with an effective amount of a pesticide, in further combination with at least one other agricultural adjuvant, in the presence or absence of a chelating agent.  
           [0102]    The present invention further provides pesticidal compositions comprising the foregoing adjuvants, combined with an effective amount of a pesticide, in further combination with at least one other agricultural adjuvant, in the presence or absence of a chelating agent, and further comprising a water-soluble salt of glyphosate.  
         DETAILED DESCRIPTION OF THE INVENTION  
         [0103]    As used in this specification and the appended claims, the word “pesticide” means any chemical substance that: 1) when applied to a given foliage which is regarded as undesirable adversely affects the longevity and/or reproductive capability of such foliage; or 2) when applied to the vicinity where insects dwell adversely affects the longevity and/or reproductive capability of such insects; or 3) is recognized by those skilled in the art as possessing pesticidal (including either insecticidal or herbicidal) properties. Include within this definition, without limitation, are those chemical materials such as: 2,4,5-T, Acephate, Acetamiprid, Acrinathrin, Aldicarb, Amitraz, Amitrole, Arsenic and its compounds, Bendiocarb, Benfuresate, Bensufliron methyl, Bentazone, BHC, 2,4-D, Bitertanol, Butamifos, Butylate, Cadusafos, Captafol(Difolatan), Captan, Carbaryl, Chinomethionat, Chlorfenvinphos, Chlorfluazuron, Chlorimuron ethyl, Chlormequat, Chlorobenzilate, Chlorpropham, Chlorpyrifos, Cinmethylin, Clofentezine, Copper terephthalate trihydrate, Cyanide compounds, Cyfluthrin, Cyhalothlin, Cyhexatin, Cypermethrin, Cyproconazole, Cyromazine, Daminozide, DCIP, DDT(including DDD,DDE), Deltamethrin, Demeton, Diazinon, Dicamba, Dichlofluanid, Dichlorvos, Diclomezine, Dicofol(Kelthane), Dieldrin( including Aldrin), Diethofencarb, Difenoconazole, Difenzoquat, Diflubenzuron, Dimethipin, Dimethoate, Dimethylvinphos, Edifenphos, Endrin, EPN, EPTC, Esprocarb, Ethiofencarb, Ethofenprox, Ethoprophos, Ethoxyquin, Etobenzanide, Etrimfos, Fenarimol, Fenbutatin oxide, Fenitrothion, Fenobucarb, Fenpyroximate, Fensulfothion, Fenthion, Fenvalerate, Flucythrinate, Flufenoxuron, Fluoroimide, Flusilazole, Flusulfamide, Flutolanil, Fluvalinate, Fosetyl, Fosthiazate, Glufosinate, Glyphosate and its water-soluble salts, Guthion, Halfenprox, Heptachlor (including Heptachlor epoxide), Hexaflumuron, Hexythiazox, Imazalil, Imazosulfuron, Imibenconazole, Iminoctadine, Inabenfide, Inorganic bromide, Iprodione, Isophenphos, Isoprocarb, Lead &amp; its compounds, Lenacil, Malathion, Maleic hydrazide, MCPA (including Phenothiol), Mepanipyrim, Mephenacet, Mepronil, Methamidophos, Methiocarb, Methoprene, Methoxychlor, Metolachlor, Metribuzin, Mirex, Myclobutanil, Nitenpyram, Oxamyl, Paclobutrazol, Parathion, Parathion-methyl, Pencycuron, Pendimethalin, Permethrin, Phenthoate, Phosalone (Rubitox), Phoxim, Picloram, Pirimicarb, Pirimiphos-methyl, Pretilachlor, Prohexadione, Propamocarb, Propiconazole, Prothiofos, Pyraclofos, Pyrazoxyfen, Pyrethrins, Pyridaben, Pyridate, Pyrifenox, Pyrimidifen, Pyriproxyfen, Quinalphos, Quinclorac, Sethoxydim, Silafluofen, Tebuconazole, Tebufenozide, Tebufenpyrad, Tecloftalam, Tefluthrin, Terbufos, Thenylchlor, Thiobencarb, Thiometon, Tralomethrin, Triadimenol, Tribenuron methyl, Trichlamide, Trichlorfon, Triclofosmethyl, Tricyclazole, Triflumizole, and Vamidothion.  
         Agricultural Adjuvants  
         [0104]    Adjuvants are chemical materials which are often employed as a component of an agriculturally active material that is to be applied to places where crops are grown or other agriculturally important land areas, and which are designed to perform specific functions, including wetting, spreading, sticking, reducing evaporation, reducing volatilization, buffering, emulsifing, dispersing, reducing spray drift, and reducing foaming. No single adjuvant can perform all these functions, but different compatible adjuvants often can be combined to perform multiple functions simultaneously; thus, adjuvants are a diverse group of chemical materials. Within the meaning of the term “Adjuvants” is included any substance added to the spray tank to modify: the performance of a pesticide contained in the spray tank either neat or in combination with other materials so as to form a spray mixture; the physical properties of the spray mixture; or both.  
           [0105]    Spray application is perhaps the weakest link in the chain of events a pesticide follows through its development process. Some researchers claim that up to 70 percent of the effectiveness of a pesticide depends on the effectiveness of the spray application. Selection of a proper adjuvant may reduce or even eliminate spray application problems associated with pesticide stability, solubility, incompatibility, suspension, foaming, drift, evaporation, volatilization, degradation, adherence, penetration, surface tension, and coverage, thereby improving overall pesticide efficiency and efficacy. Thus, by increasing the performance of an adjuvant composition, the likelihood for successful application of the pesticide is dramatically increased.  
           [0106]    Surfactant adjuvants physically alter the surface tension of a spray droplet. For a pesticide to perform its function properly, a spray droplet must be able to “wet” the foliage and spread out evenly over a leaf. Surfactants enlarge the area of pesticide coverage, thereby increasing the pest&#39;s or leaf&#39;s exposure to the chemical. Without proper wetting and spreading, spray droplets may merely run off, or otherwise fail to adequately cover these surfaces. Such surfactant adjuvants enhance the absorbing, emulsifying, dispersing, spreading, sticking, wetting or penetrating properties of pesticides. Surfactants are most often used with herbicides to help a pesticide spread over and penetrate the waxy outer layer of a leaf or to penetrate through the small hairs present on a leaf surface.  
           [0107]    While surfactant adjuvants may be anionic, cationic, or nonionic, the nonionic surfactants are in most common usage. The “multi-purpose” nonionic surfactants can be composed of alcohol and fatty acid ethoxylates, have no electrical charge and are compatible with most pesticides. Certain other surfactants may be cationic (+ charge) or anionic (− charge) and are specialty adjuvants that are used in specific situations and with specific products. Anionic surfactants are mostly used with acids or salts, and are more specialized and used as dispersants and compatibility agents. Cationic surfactants are used less frequently but one group, the ethoxylated fatty amines, sometimes are used with the herbicide glyphosate.  
           [0108]    Silicone-based surfactants are increasing in popularity due to their superior spreading ability. Some of these surfactants are a blend of nonionic surfactants (MS) and silicone while others are entirely a silicone. The combination of a NIS and a silicone surfactant can increase absorption into a plant so that the time between application and rainfall can be shortened. There are generally two types of organo-silicone surfactants: the polyether-silicones that are soluble in water and the alkyl-silicones that are soluble in oil. Unlike polyether-silicone types, alkyl-silicone surfactants work well with oil-based sprays, such as dormant and summer oil sprays used in insect control. Alkyl-silicone-enhanced oil sprays can maximize insecticidal activity and even allow significantly lower pesticide use rates that reduce residue levels on crops.  
           [0109]    Sticker adjuvants increase the adhesion of solid particles to target surfaces. These adjuvants can decrease the amount of pesticide that washes off during irrigation or rain. Stickers also can reduce evaporation of the pesticide and some slow ultraviolet (UV) degradation of pesticides. Many adjuvants are formulated as spreader-stickers to make a general purpose product that includes a wetting agent and an adhesive.  
           [0110]    Extender adjuvants function like sticker surfactants by retaining pesticides longer on the target area, slowing volatilization, and inhibiting UV degradation.  
           [0111]    Plant penetrant surfactants have a molecular configuration that enhances penetration of some pesticides into plants. A surfactant of this type may increase penetration of a pesticide on one species of plant but not another. Systemic herbicides, auxin-type herbicides, and some translocatable fungicides can have their activity increased as a result of enhanced penetration.  
           [0112]    Compatibility agent adjuvants are especially useful when pesticides are combined with liquid fertilizers or other pesticides, particularly when the combinations are physically or chemically incompatible, such as in cases when clumps and/or uneven distribution occurs in the spray tank. A compatibility agent may eliminate problems associated with such situations.  
           [0113]    Buffers or pH modifier adjuvants are generally employed to prevent problems associated with alkaline hydrolysis of pesticides that are encountered when the pH of a pesticide exceeds about 7.0 by stabilizing the pH at a relatively constant level. Extreme pH levels in the spray mixture can cause some pesticides to break down prematurely. This is particularly true for the organophosphate insecticides but some herbicides can break down into inactive compounds in a matter of hours or minutes in alkaline situations (pH&gt;7). For example, the insecticide Cygon (dimethoate) loses 50 percent of its pest control power in just 48 minutes when mixed in water of pH 9. At a pH of 6, however, it takes 12 hours for degradation to progress to that extent. On the other hand, sulfonyl urea (SU) herbicides tend to break down more rapidly where the pH is below 7. At low pHs, the herbicide 2,4-D is an uncharged molecule. At higher pH, 2,4-D tends to become more anionic or negatively charged which can affect its movement in the environment. Leaf coatings often have a high pH that can contribute to poor performance with certain herbicides. The use of a buffering or acidifying adjuvant can stabilize or lower the pH of a spray solution thereby improving the stability of the pesticide being used.  
           [0114]    Mineral control adjuvants are used to mask the problems associated with water hardness minerals in spray water which can diminish the effectiveness of many pesticides. Mineral ions such as calcium and magnesium salts such as carbonates, chlorides, etc., are commonly found in hard water. These ions can bind with the active ingredients of some pesticides, especially the salt-formulation herbicides such as Roundup™ (glyphosate), Poast™ (sethoxydim), Pursuit™ (imazethapyr), and Liberty™ (glufosinate) resulting in poor weed control. The use of water-conditioning or mineral control adjuvants gives hard water minerals something to bind with other than the herbicide. In addition, some ammonium sulfate-based adjuvants can be used to offset hard water problems.  
           [0115]    Drift retardant adjuvants improve on-target placement of pesticide spray by increasing the average droplet size, since drift is a function of droplet size with drops with diameters of 100 microns or less tending to drift away from targeted areas.  
           [0116]    Defoaming agent adjuvants are used to control the foam or frothy head often present in some spray tanks that results from the surfactant used and the type of spray tank agitation system can often can be reduced or eliminated by adding a small amount of foam inhibitor.  
           [0117]    Thickener adjuvants increase the viscosity of spray mixtures which afford control over drift or slow evaporation after the spray has been deposited on the target area.  
           [0118]    Oil-based adjuvants have been gaining in popularity especially for the control of grassy weeds. There are three types of oil-based adjuvants: crop oils, crop oil concentrates (COC) and the vegetable oils. Crop Oil adjuvants are derivative of paraffin-based petroleum oil. Crop oils are generally 95-98% oil with 1 to 2% surfactant/emulsifier. Crop oils promote the penetration of a pesticide spray either through a waxy plant cuticle or through the tough chitinous shell of insects. Crop oils may also be important in helping solubilize less water-soluble herbicides such as Poast™ (sethoxydim), Fusilade™ (fluaziprop-butyl) and atrazine. Traditional crop oils are more commonly used in insect and disease control than with herbicides. Crop oil concentrates (COC) are a blend of crop oils (80-850%) and the nonionic surfactants (15-20%.). The purpose of the nonionic surfactant in this mixture is to emulsify the oil in the spray solution and lower the surface tension of the overall spray solution. Vegetable oils work best when their lipophilic characteristics are enhanced, and one common method of achieving this is by esterification of common seed oils such as rapeseed, soybean, and cotton. The methylated seed oils (MSO) are comparable in performance to the crop oil concentrates, in that they increase penetration of the pesticide. In addition, silicone-based MSOs are also available that take advantage of the spreading ability of the silicones and the penetrating characteristics of the MSOs.  
           [0119]    The special purpose or utility adjuvants are used to offset or correct certain conditions associated with mixing and application such as impurities in the spray solution, extreme pH levels, drift, and compatibility problems between pesticides and liquid fertilizers. These adjuvants include acidifiers, buffering agents, water conditioners, anti-foaming agents, compatibility agents, and drift control agents.  
           [0120]    Fertilizer-based adjuvants, particularly nitrogen-based liquid fertilizers, have been frequently added to spray solutions to increase herbicide activity. Research has shown that the addition of ammonium sulfate to spray mixtures enhances herbicidal activity on a number of hard-to-kill broadleaf weeds. Fertilizers containing ammonium nitrogen have increased the effectiveness of the certain polar, weak acid herbicides such as Accent™ (nicosulfuron), Banvel™ (dicamba), Blazer™ (acifluorfen-sodium), Roundup™ (glyphosate), Basagran™ (bentazon), Poast™ (sethoxydim), Pursuit™ (imazethapyr), and 2,4-D amine. Early fertilizer-based adjuvants consisted of dry (spray-grade) ammonium sulfate (AMS) at 17 lbs per 100 gallons of spray volume (2%). Studies of these adjuvants has shown that Roundup™ uptake was most pronounced when spray water contained relatively large quantities of certain hard water ions, such as calcium, sodium, and magnesium. It is thought that the ions in the fertilizer tied up the hard water ions thereby enhancing herbicidal action.  
           [0121]    Polyfunctional acids are also often used in pesticide formulations as pH buffers and chelants. A large number of polyfunctional acids are known to those skilled in the art, and the following exemplary list should not be construed as being delimitive in any way of the possible polyfunctional acids which may be included in an adjuvant or pesticide composition according to the invention: phthalic acid, isophthalic acid, terephthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, hemimellitic acid, trimellitic acid, trimesic acid, phosphoric acid, and sulfuric acid.  
           [0122]    Thus, the words “agricultural adjuvant” when used in this specification and the appended claims means any material recognized by those skilled in the art of pesticides to be useful as an adjuvant material in connection with the formulation and/or use of a pesticide, and include all materials falling within each of the specific classes of adjuvant outlined above.  
         Pesticide Formulations  
         [0123]    The following mixtures were prepared by mechanical mixing of the indicated ingredients until a homogeneous solution resulted: 
       
    
    
     EXAMPLE 1  
       [0124]    [0124]                                                       Glyphosate (62%)   68.0           SURFONIC ® T-5   5.0           SURFONIC ® ADA-170   5.0           Water   14.0           Diethylene Glycol   8.0           total   100.0                        
       EXAMPLE 2  
       [0125]    [0125]                                                       Glyphosate (62%)   68.0           SURFONIC ® T-5   4.0           SURFONIC ® ADA-170   4.0           Citric Acid   2.0           Water   14.0           Diethylene Glycol   8.0           total   100.0                        
       Adjuvant Composition  
       [0126]    [0126]                                                       SURFONIC ® ADA-170   75.00           TERIC ® 204   25.00           total   100.00                        
         [0127]    SURFONIC® T-5 is a 5-mole EO average tallow amine ethoxylate available from Huntsman Petrochemical Corporation of Austin, Tex. SURFONIC® ADA-170 is an ethylene diamine alkoxylate available from Huntsman Petrochemical Corporation of Austin, Tex. TERIC® 204 is a tallow amine ethoxylate available from Huntsman Chemical Company Australia Pty Ltd. In order to provide an adjuvant composition according to the invention, one merely mixes the components together using conventional mixing equipment, until a homogeneous mixture is formed.  
         [0128]    Several blends were evaluated as adjuvant compositions for use with glyphosate, using a greenhouse testing protocol. The glyphosate concentrates were formulated at 7.5 w/w% surfactant, according to the formula in Table 1:  
                                           TABLE 1                           Glyphosate Concentrate Formulation                    Loading           Component   w/w %                            Glyphosate IPA salt   66.1           (62.0% a.i.)           Surfactant Blend   7.5           Water   26.4                      
 
         [0129]    The glyphosate formulations were applied at the rate of 16 oz/acre at a spray rate of 10 gal/acre. Four replicates were run and visual necrosis was recorded at 21 days after treatment DAT). Velvetleaf (Abutilon Theophrasti Medik.) was sprayed at the 4-6 inch stage, and common lambsquarters (Chenopodium Album L.) was sprayed at the 4-7 inch stage. The individual adjuvant surfactant chemistries tested are listed in Table 2:  
                                                           TABLE 2                           Individual Adjuvant Surfactant Chemistries                            Moles       Adjuvant   Surfactant       Moles Ethylene   Propylene       Sample   Chemistry   Hydrophobe   Oxide   Oxide                    A   Polyoxyalkylene alkylamine   Tallow amine   15   0       B   Polyoxyalkylene alkyldiamine   Ethylene   22   4           Propoxylated, Ethoxylated   diamine       C   Polyoxyalkylene alkyldiamine   Ethylene   22   4           Ethoxylated, Propoxylated   diamine       D   Polyoxyalkylene alkyldiamine   Ethylene   22   4           Ethoxylated, Alkoxylated   diamine       E   Polyetheramine alkoxylate   Alkyl   5   2               etheramine                  
 
         [0130]    Table 3 shows the weed killing performance of blends of polyoxyalkylene alkylamine adjuvants with polyoxyalkylene alkyldiamine adjuvants versus the efficacy of the individual components:  
                                     TABLE 3                           Efficacy of Polyoxyalkylene Alkylamine &amp;       Polyoxyalkylene Alkyldiamine Blends.                Glyphosate                   Adjuvant   Formulation   Velvetleaf   Lambsquarters   Average       Sample   Cloud Point   Control (%)   Control (%)   Weed       Chemistry   (° C.)   21 DAT   21 DAT   Control               A   —   71   67   69       B   —   70   50   60       D   —   70   55   63       67% B + 33% A   89   87   78    83*       67% D + 33% A   82   79   69   74                          
 
         [0131]    Table 4 shows the weed killing performance of a blend of a polyetheramine alkoxylate adjuvant with a polyoxyalkylene alkyldiamine adjuvant versus the efficacy of the individual components:  
                                     TABLE 4                           Efficacy of a Polyetheramine &amp; Polyoxyalkylene       Alkyldiamine Blend            Adjuvant   Glyphosate   Velvetleaf   Lambsquarters   Average       Sample   Formulation   Control (%)   Control (%)   Weed       Chemistry   Cloud Point (° C.)   21 DAT   21 DAT   Control               C   87   77   59   68       E   93   69   79   74       67% C +   95   90   74   82       33% E                  
 
         [0132]    There are several synergies shown in Tables 3 and 4. The overall efficacy of the adjuvant chemistry blends is greater than any of the individual components. The high cloud points of the glyphosate formulations based on the adjuvant blends show that these products could successfully contain a higher loading of glyphosate. Cloud points of commercial products can be as low as 60° C., so there is room for increasing the amount of glyphosate in products based on these blends.  
         [0133]    Zein testing was performed on the blends to evaluate irritancy potential. All of the blends were measured as non-irritants. The polyoxyalkylene alkylamine adjuvants by themselves are classified as moderate to severe irritants depending on the degree of ethoxylation. The polyoxyalkylene alkyldiamine adjuvant chemistry can be blended with the polyoxyalkylene alkylamine adjuvant chemistry to lower the blend irritancy, raise the glyphosate loading potential, and still yield high efficacy.  
         [0134]    The efficacy and formulation data combined with the toxicity results show that the adjuvant blends disclosed in this invention will allow development of novel glyphosate formulations which combine high efficacy, high pesticide loading, and low toxicity.  
         [0135]    Consideration must be given to the fact that while the present invention has been disclosed and described with respect to certain embodiments, it is nevertheless to be understood that alterations and modifications to the present invention that yield substantially equivalent results shall become apparent to those of ordinary skill in the art after their reading and understanding this specification and its appended claims. Accordingly, the scope of the present invention includes all such alterations and modifications, and is limited only by the scope of the claims which now follow: