Non-aqueous organo liquid delivery systems containing dispersed poly (organic acids) that improve availability of macro and micro-nutrients to plants

Abstract

The present invention relates to improving the efficiency of man-made and/or natural organic-based animal manure fertilizers by administration of formulations containing poly(organic acids), [P(OA)]s, and/or their salts dispersed in a Non-aqueous Organic Solvent Delivery System (NOSDS). Utilizing a NOSDS allows for coating all components in a fertilizer formulation including but not limited to Urea, Manure, mono-ammonium phosphate (MAP), di-ammonium phosphate (DAP), solid micronutrients such as lime, zinc chloride, etc.) with a layer of [P(OA)]s and/or their salts that liberates, in a plant available form, the micronutrient metals and macronutrients, that are bound as insoluble salts and complexes in the soil. The carboxylic groups of a [P(OA)] that can exist within the [P(OA)] as carboxylic acids, carboxylic anhydrides and/or carboxylic imides, dispersed within the NOSDS, can be neutralized with one or more metals in the form of elemental metals, metal oxides, metal hydroxides, metal alkylates and metal carbonates and/or nitrogen containing compounds such as ammonia, ammonium hydroxide or organoamines to form a stable dispersion that can contain completely complexed micronutrients and provide the vehicle for the delivery of these nutrients to soils and/or as a coating to the surfaces fertilizer granules and seeds.

Claims

1. A composition comprising one or more Poly (organic acids), [P(OA)]s, and/or their salt(s) dissolved in one or more of a Non-aqueous Organo Solvent Delivery System (NOSDS), wherein said composition is a stable dispersion for coating man-made and/or natural fertilizer components and/or seeds wherein the [P(OA)]s are homopolymers, copolymers and/or terpolymers and wherein said homopolymers, copolymers and/or terpolymers are comprised of one or more of the following monomers: aspartic acid, glutamic acid, maleic acid, itaconic acid, citraconic acid, citric acid, acrylic acid, methacrylic acid, itaconic acid, and citraconic acid, their C.sub.1-6esters, anhydrides, and imides, or their salts; and wherein the NOSDS is comprised of: a) one or more protic solvents selected from the group consisting of: 1) a C1-10 alcohol, 2) one or more polyols selected from the group consisting of trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, and glycerin, 3) poly(C1-10 alkylene) glycols, 4) one or more alkylene glycols selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, and butylene glycol, 5) isopropylidene glycerol 6) one or more alkylene glycol alkyl ethers selected from the group consisting of tripropylene glycol methyl ether, tripropylene glycol butyl ether, dipropylene glycol butyl ether and dipropylene glycol butyl ether, 7) ethyl, propyl, or butyl lactate, 8) one or more alkanolamines selected from the group consisting of ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine and 9) glycerol carbonate and b) one or more aprotic solvents selected from the group consisting of 1) dimethyl sulfoxide 2) a dialkyl sulfoxide, diaryl sulfoxide, or an alkylaryl sulfoxide having the formula:
R.sub.1S(O).sub.xR.sub.2 wherein R.sub.1 and R.sub.2 are each independently a C.sub.1-6 alkyl group, an aryl group, or C.sub.1-3alkylenearyl group, or R.sub.1 and R.sub.2 with the sulfur to which they are attached form a 4 to 7membered ring wherein R.sub.1 and R.sub.2 together are a C.sub.1-6 alkylene group which optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N, and P in the ring and x is 1 or 2 or 3) an alkylene carbonate selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate, 4) a polyol capped with acetate or formate wherein the polyol portion is one or more of ethylene glycol, 1,3 propylene glycol, 1,2propylene glycol, butylene glycol, trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose or glycerin, 5) an alkylene glycol alkyl ether acetates selected from the group consisting of dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether acetate, and tripropylene glycol butyl ether acetate, 6) isophorone, 7) one or more members selected from the group consisting of dimethylsuccinate, dimethyl adipate, diethyl glutarate, and dimethyl glutarate, 8) one or more members selected from the group consisting of dimethylacetamide, dimethylformamide, and dimethyl-2-imidazolidinone 9) hexamethylphosphoramide, 10) one or more members selected from the group consisting of 1,2-dimethyloxyethane and 2-methoxyethyl ether, 11) cyclohexylpyrrolidone and 12) limonene and wherein the composition is substantially free of water.

2. The composition of claim 1, wherein the salts are derived from metals, metal hydroxides, metal alkylates, metal carbonates, ammonia, ammonium hydroxide, or organoamines.

3. The composition of claim 2, wherein the metals in the metals, metal hydroxides, metal alkylates, or metal carbonates comprise one or more of Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo or Ni.

4. The composition of claim 2, wherein the organoamines comprise one or more of mono C.sub.1-6 amine, di C.sub.1-6 amine, tri C.sub.1-6 amine, mono ethanol amine, diethanol amine, triethanol amine, monoisopropanol amine, diisopropanol amine, triisopropanol amine, ethylene diamine diethylene triamine, triethylene tetraamine, or tetraethylene pentamine.

5. The composition of claim 1, wherein the composition comprises one or more protic solvents or one or more aprotic solvents.

6. The composition of claim 1, wherein the composition: i has flashpoints above 145 F.; ii has a human health rating of 1.0; iii provides stable dispersions of [P(OA)]s or their salts at levels of 1 -50% in the NOSDS at storage temperatures down to at least 10 C.; iv provides improved, even application of a coating to fertilizer granules and seeds while not causing clumping of the fertilizer granules, premature seed germination and does not support the growth of mold and mildew on seeds; and v will not detrimentally impact the stability of alkyl thiophosphoric triamides.

7. The composition of claim 1, wherein the NOSDS comprises one or more protic solvents wherein the [P(OA)]s to the one or more protic solvent ratio is between about 90/10to 10/90.

8. The composition of claim 1, wherein the one or more [P(OA)]s comprises a potassium salt of a polyaspartate wherein the potassium salt of the polyaspartate is present in an amount that is between about 10-45% of a total composition amount and the NOSDS of the formulation is ethylene glycol.

9. The composition of claim 1, further comprising one or more of surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, dispersed urease inhibitor(s), dispersed nitrification inhibitor(s), pesticide(s), fungicides(s), herbicide(s), insecticide(s) or flow modifiers.

10. A process for producing the composition of claim 1, wherein said process comprises procuring one or more of the following monomers: aspartic acid, glutamic acid, maleic acid, itaconic acid, citraconic acid, citric acid, acrylic acid, methacrylic acid, itaconic acid, and citraconic acid, their anhydrides, and imides, or their salts; wherein said one or more monomers is/are dispersed into one or more protic solvents at a molar ratio range of about 0.5/1 to 10/1 of NOSDS/ monomer and/or at a weight ratio of 10/90% to 90/10% of monomer/protic solvent which is heated to 120-190 C. to form an ester wherein the one or more protic solvents are selected from the group consisting of: 1) an alcohol from the family of C.sub.1-10 alkanols, 2) polyols selected from the group consisting of trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, and glycerin, 3) poly(C.sub.1-10 alkylene) glycols, 4) alkylene glycols selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, and butylene glycol, 5) isopropylidene glycerol 6) alkylene glycol alkyl ethers selected from the group consisting of tripropylene glycol methyl ether, tripropylene glycol butyl ether, dipropylene glycol butyl ether and dipropylene glycol butyl ether, 7) ethyl, propyl, or butyl lactate, 8) an alkanolamine selected from the group consisting of ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine and 9) glycerol carbonate; and heating said dispersion to a polymerization temperature with or without catalyst, until a molecular weight of 1500 to 10000 g/mol is achieved wherein water is removed with a vacuum of 200 mm or less thereby resulting in a composition comprising one or more Poly (organic acids), [P(OA)]s, and/or their salt(s) dissolved in one or more protic NOSDS, wherein said composition is a stable dispersion for coating man-made and natural fertilizer components and/or seeds and wherein the composition is substantially free of water, and to which one or more aprotic solvents is added wherein said aprotic solvents comprise one or more members selected from the group consisting of 1) dimethyl sulfoxide 2) dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:
R.sub.1S(O).sub.xR.sub.2 wherein R.sub.1 and R.sub.2 are each independently a C.sub.1-.sub.6 alkylene group, an aryl group, or C.sub.1-.sub.3alkylenearyl group or R.sub.1 and R.sub.2 with the sulfur to which they are attached form a 4 to 7membered ring wherein R.sub.1 and R.sub.2 together are a C.sub.1-.sub.6 alkylene group which optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N, and P in the ring and x is 1 or 2; 3) alkylene carbonates selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate, 4) polyols capped with acetate or formate wherein the polyol is one or more of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol, trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose and/or glycerin, 5) alkylene glycol alkyl ethers acetates selected from the group consisting of dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether acetate, and tripropylene glycol butyl ether acetate, 6) isophorone, 7) dimethylsuccinate, dimethyl adipate, diethyl glutarate, dimethyl glutarate, 8) dimethylacetamide, dimethylformamide, dimethyl-2-imidazolidinone 9) hexamethylphosphoramide, 10) 1,2-dimethyloxethane, 2-methoxyethyl ether, 11) cyclohexylpyrrolidone and 12) limonene wherein said composition is a stable dispersion for coating man-made and natural fertilizer components and/or seeds and wherein the composition is substantially free of water.

11. The process of claim 10, wherein said ester is further saponified generating a carboxylic acid salt wherein said salt is derived from metals, metal hydroxides, metal alkylates, metal carbonates, ammonia, ammonium hydroxide, or organoamines wherein water resulting from neutralization or from addition of aqueous solutions of alkalis is removed by stripping by elevated temperature or through a combination of temperature and vacuum , molecular sieves , drying agents and/or filtration.

12. The process of claim 11, wherein a metal in the metals, metal hydroxides, metal alkylates, or metal carbonates is Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo and/or Ni.

13. The process of claim 11, wherein the organoamines comprise one or more of mono C.sub.1-6 amine, di C.sub.1-6 amine, tri C.sub.1-6 amine, mono ethanol amine, diethanol amine, triethanol amine, monoisopropanol amine, diisopropanol amine, triisopropanol amine, ethylene diamine diethylene triamine, triethylene tetraamine, or tetraethylene pentamine.

14. A process for producing a composition wherein said process comprises procuring one or more of the following monomers: aspartic acid, glutamic acid, maleic acid, itaconic acid, citraconic acid, citric acid, acrylic acid, methacrylic acid, itaconic acid, and citraconic acid, their C.sub.1-6esters, anhydrides, and imides, or their salts; and dispersing said one or more monomers into an aprotic solvent to create a dispersion wherein said aprotic solvent is one or more members selected from the group consisting of 1) dimethyl sulfoxide 2) dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:
R.sub.1S(O).sub.xR.sub.2 wherein R.sub.1 and R.sub.2 are each independently a C.sub.1-.sub.6 alkylene group, an aryl group, or C.sub.1-.sub.3alkylenearyl group or R.sub.1 and R.sub.2 with the sulfur to which they are attached form a 4 to 8membered ring wherein R.sub.1 and R.sub.2 together are a C.sub.1-.sub.6 alkylene group which optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N, and P in the ring and x is 1 or 2; 3) an alkylene carbonate selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate, 4) a polyol capped with acetate or formate wherein the polyol is one or more of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol, trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose and glycerin, 5) an alkylene glycol alkyl ether acetate selected from the group consisting of dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether acetate, and tripropylene glycol butyl ether acetate, 6) isophorone, 7) dimethylsuccinate, dimethyl adipate, diethyl glutarate, dimethyl glutarate, 8) dimethylacetamide, dimethylformamide, dimethyl-2-imidazolidinone 9) hexamethylphosphoramide, 10) 1,2-dimethyloxethane, 2-methoxyethyl ether, 11) cyclohexylpyrrolidone and 12) limonene; heating said dispersion to a polymerization temperature with or without a catalyst, held at polymerization temperature until a molecular weight of 1500 to 10000 grams/mol is achieved, wherein water is removed by a vacuum of 200 mm or less, thereby resulting in a composition comprising one or more Poly (organic acids), [P(OA)]s, and/or their salt(s) dissolved in one or more aprotic NOSDS, wherein said composition is a stable dispersion for coating man-made and natural fertilizer components and/or seeds, and further resulting in a composition that is substantially free of water.

15. The process of claim 14, further comprising neutralizing the one or more monomers with one or more metals, wherein said one or more metals comprise elemental metals, metal oxides, metal hydroxides, metal alkylates or metal carbonates, or with one or more nitrogen containing compounds comprising ammonia, ammonium hydroxide, or organoamines wherein water resulting from neutralization or from addition of aqueous solutions of alkalis is removed by stripping the composition by using an elevated temperature or by a combination of temperature with vacuum , by molecular sieves , or by drying agents and filtration.

16. The process of claim 15, wherein the one or more metals in the elemental metals, metal oxides, metal hydroxides, metal alkylates or metal carbonates comprise Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo or Ni.

17. The process of claim 15, wherein the organoamines comprise one or more of mono C.sub.1-6 amine, di C.sub.1-6 amine, tri C.sub.1-6 amine, mono ethanol amine, diethanol amine, triethanol amine, monoisopropanol amine, diisopropanol amine, triisopropanol amine, ethylene diamine diethylene triamine, triethylene tetraamine, or tetraethylene pentamine.

18. A process for producing a composition wherein said process comprises procuring a polymer that comprises polysuccinimide, polyaspartic acid, polyglutamic acid, and/or a copolymer of aspartic acid and glutamic acid and/or salts thereof; wherein said polymer is dispersed within a NOSDS at a % weight ratio of 10:90% to 90:10% of polymer:NOSDS, wherein the NOSDS comprises a) one or more protic solvents which are heated to 120-190 C. to form an ester and wherein the one or more protic solvents are selected from the group consisting of:: 1) an alcohol from the family of C.sub.1-10 alkanols , 2) polyols selected from the group consisting of trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, and glycerin, 3) poly(C.sub.1-10 alkylene) glycols, 4) alkylene glycols selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, and butylene glycol, 5) isopropylidene glycerol 6) alkylene glycol alkyl ethers selected from the group consisting of tripropylene glycol methyl ether, tripropylene glycol butyl ether, dipropylene glycol butyl ether and dipropylene glycol butyl ether, 7) ethyl, propyl, or butyl lactate, 8) an alkanolamine selected from the group consisting of ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine and 9) glycerol carbonate wherein water is removed through a vacuum of 200 mm or less thereby resulting in a composition comprising one or more Poly (organic acids), [P(OA)]s, and/or their salt(s) dissolved in one or more protic NOSDS, wherein said composition is a stable dispersion for coating man-made and natural fertilizer components and/or seeds and wherein the composition is substantially free of water.

19. The process of claim 18, wherein the ester is saponified generating a carboxylic acid salt wherein said salt is derived from metals, metal hydroxides, metal alkylates, metal carbonates, ammonia, ammonium hydroxide, or organoamines wherein water resulting from neutralization or from addition of aqueous solutions of alkalis is removed by stripping at elevated temperature or a combination of temperature and vacuum, molecular sieves, drying agents and filtration.

20. The process of claim 19, wherein the salts are derived from metals, metal hydroxides, metal alkylates, metal carbonates, ammonia, ammonium hydroxide, or organoamines and the metal in the metals, metal hydroxides, metal alkylates, or metal carbonates are one or more of Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo or Ni.

21. The process of claim 20, wherein the organoamines comprise one or more of mono C.sub.1-6 amine, di C.sub.1-6 amine, tri C.sub.1-6 amine, mono ethanol amine, diethanol amine, triethanol amine, monoisopropanol amine, diisopropanol amine, triisopropanol amine, ethylene diamine diethylene triamine, triethylene tetraamine, or tetraethylene pentamine.

Description

EXAMPLE 1

(1) 400 grams of ethylene glycol was charged to a vessel, placed under strong agitation and then heated to 60 C. 222.2 grams of polyaspartate-potassium salt/90% NVS was then slowly charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was placed under high shear agitation by using an overhead mixer equipped with a cowles blade while maintaining the batch temperature at 60-80 C. for 1 hour. After one hour the vessel was sealed and a vacuum of 200 mm or less was pulled to remove water. The mixture was cooled to <30 C. and then packaged off in an appropriate container.

EXAMPLE 2

(2) 120 grams of Example 1 was heated to 60 C., placed under agitation and then 80 grams of propylene glycol was charged to the vessel. The combination was mixed for 30 minutes and then cooled to <40 C. and packaged off.

EXAMPLE 3

(3) 120 grams of Example 1 was heated to 60 C., placed under agitation and then 80 grams of glycerin were charged to the vessel. The combination was mixed for 30 minutes and then cooled to <40 C. and packaged off.

EXAMPLE 4

(4) 120 grams of Example 1 was heated to 60 C., placed under agitation and then 40 grams of ethylene glycol and 40 grams of tripropylene glycol monomethyl ether were charged to the vessel. The combination was mixed for 30 minutes and then cooled to <40 C. and packaged off.

EXAMPLE 5

(5) 450 grams of ethylene glycol was charged to a vessel, placed under strong agitation and then heated to 60 C. 300 grams of a polysuccinimide (5000 average molecular weight) was then slowly charged to the vessel and mixed until completely dispersed. The mixture was then heated to 140 C. and held until all particles dissolved (1.5 hrs). The mix was then cooled to 50 C. 147 grams of KOH flakes were slowly charged to the mix at a rate to maintain temperature of 60-80> C. The formulation was mixed until all KOH flakes (100%) were dissolved. The mix was then cooled to 40 C. and then placed under high shear agitation by using an overhead mixer equipped with a cowles blade while maintaining the batch temperature at 60-80 C., for 1 hour. After one hour, an FTIR scan was run to determine if the presence of ester had been eliminated. The mixture was sampled every 30 minutes until traces of esters had been eliminated. The mixture was cooled to <30 C. and then packaged off in an appropriate container.

EXAMPLE 6

(6) 58.54 grams of Example 5 was charged to a vessel and then placed under strong agitation and then heated to 60 C. 65.4 grams of ethylene glycol were then charged to the vessel and mixed for 30 minutes. After 30 minutes, the mixture was cooled to 38 C. and then packaged off in an appropriate container.

EXAMPLE 7

(7) 58.54 grams of Example 5 was charged to a vessel and then placed under strong agitation and then heated to 60 C. 35.4 grams of ethylene glycol and 30 grams of dimethyl glutarate were then charged to the vessel and mixed for 30 minutes. After 30 minutes, the mixture was cooled to 38 C. and then packaged off in an appropriate container.

EXAMPLE 8

(8) 58.54 grams of Example 5 was charged to a vessel and then placed under strong agitation and then heated to 60 C. 65.4 grams of glycerin were then charged to the vessel and mixed for 30 minutes. After 30 minutes, the mixture was cooled to 38 C. and then packaged off in an appropriate container.

EXAMPLE 9

(9) 104.3 grams of Example 5 was charged to a vessel and then placed under strong agitation and then heated to 60 C. 45.7 grams of ethylene glycol were then charged to the vessel and mixed for 30 minutes. After 30 minutes, the mixture was cooled to 38 C. and then packaged off in an appropriate container.

EXAMPLE 10

(10) 183.12 grams of dimethyl sulfoxide was charged to a vessel, placed under strong agitation and then heated to 60 C. 78.48 grams of a polysuccinimide (5000 average molecular weight) was then slowly charged to the vessel and mixed until completely dispersed. 72.74 grams of DI water was charged to the vessel and then 49.07 grams of NH4OH/28% were slowly charged holding the mixture's temperature at 60-80 C. It was mixed for one hour and then placed under a vacuum of 50 mm with a slight N.sub.2 sparge until distillation ceases. The mix was then cooled to 40 C. and then packaged off in an appropriate container.

EXAMPLE 11

(11) 282.52 grams of dimethyl sulfoxide was charged to a vessel, placed under strong agitation and then heated to 60 C. 146.23 grams of a partial sodium hydroxide neutralized polyacrylic acid (Kemira 5847) was then charged to the vessel and mixed for 15 minutes. A vacuum of 38 mm was applied until distillation ceases. The mix was then cooled to 40 C. and then packaged off in an appropriate container.

EXAMPLE 12

(12) 150 grams of ethylene glycol, 150 grams of L-aspartic acid and 1.5 grams of phosphoric acid/85% were charged to a vessel, then placed under strong agitation and then heated to 185 C. After 5 hrs, 64.3 grams of distillate were collected and the batch was cooled to 60 C. 97.44 grams KOH flake (100%) was then slowly charged to the vessel at a rate that allowed the batch temperature to be 60-80 C. and mixed until completely dissolved. It was then placed under high shear agitation by using an overhead mixer equipped with a cowles blade while maintaining the batch temperature at 60-80 C. for 1 hour. After one hour, an FTIR scan was run to determine if the presence of ester had been eliminated. The mixture was sampled every 30 minutes until traces of esters had been eliminated. After the ester peak was eliminated, 281.08 grams of ethylene glycol were charged and the resulting mixture was mixed for 30 minutes. The mix was then cooled to 40 C. and then packaged off in an appropriate container.

EXAMPLE 13

(13) 71.58 grams of acetone was charged to a vessel and then 12.48 grams of maleic anhydride and 16.49 grams itaconic anhydride and 0.98 grams of benzoyl peroxide were charged to the vessel. Very slow agitation was used until the maleic briquettes were dissolved. The vessel was then sealed and inerted with N.sub.2 and the batch was heated to 60 C. and held at 55-65 C. for five hours. After five hours, the batch was cooled to 35 C. and 43.45 grams of ethylene glycol was charged. A vacuum was then pulled on the vessel slowly decreasing the pressure based on the distillation rate while heating the batch back to 55-65 C. When distillation ceases, the vacuum was broken with N.sub.2 and then 15.39 grams of KOH flake (100%) were slowly charged in order to hold temperature at 60-80 C. When KOH flakes were completely dissolved, the mix was placed under high shear agitation by using an overhead mixer equipped with a cowles blade while maintaining the batch temperature at 60-80 C. for 1 hour. Thereafter the mix was checked using an FTIR scan. The FTIR scan was run and checked every 30 minutes for the disappearance of the ester peak. After the ester peak disappeared, 89.63 grams of ethylene glycol were charged, and the batch was then mixed 30 minutes and cooled to <40 C. and then off-loaded into the appropriate container.

EXAMPLE 14

(14) 45 grams of Example 12 were mixed with 10 grams of N-Yield (a urease inhibitor in a non-aqueous liquid), 40 grams of N-Bound (a nitrification inhibitor in a non-aqueous liquid) and 5 grams of glycerin. The resulting fluid product was then off-loaded into the appropriate container.

EXAMPLE 15

(15) 99.5 grams of DMSO, 99.5 grams of l-aspartic acid and 1.0 grams of phosphoric acid/85% were charged to a vessel, then placed under strong agitation and then heated to 155 C. After 4.5 hrs. 28.49 grams of distillate were collected and the batch was cooled to 80 C. 85.09 grams NH.sub.4OH (28%) was then slowly charged to the vessel at a rate that allowed the batch temperature to be 60-80 C. over a 5 hour period. The reactor was sealed and heated to 95 C and held for 17 hrs and then checked by IR to insure the ester was eliminated. 352.88 gms of DMSO were charged and then heated back to 80 C, 68.07 gms of DCD were charge and mixed until particles dissolved. The batch was cooled to 35 C and then 17.02 NBPT were charged and mixed until particles dissolved. 51.05 gms of propylene glycol were charged and mix 15 minutes. The mixture was then package and 50 gins placed in a 50 C oven for 3 days. After 3 days at 50 C, the product showed no signs of instability.

EXAMPLE 16

(16) 43.57 grams of polysuccinimide (molecular weight 3000-5000), 119.12 grams of ethylene glycol were charged to a reactor, placed under agitation and heated to 140 C. until all particles were solubilized. 2.41 grams of zinc oxide were charged while holding temperature at 120 C. until appearance of mixture transitioned from milky to translucent. The reactor was then cooled to 40 C and 19.19 of KOH/45% were slowed charged while holding the temperature less than 80 C. The product was then cooled to <40 C. and packaged off.

EXAMPLE 17

(17) 250 grams of ethylene glycol, 250 grams of L-aspartic acid and 2.94 grams of phosphoric acid/85% were charged to a vessel, then placed under strong agitation and then heated to 150 C. After 5 hours no particles were observed and 67.6 grams of distillate were collected. The batch was cooled to 120 C. and 23.67 grams of magnesium oxide was slowly charged and dispersed with 15 minutes if agitation. 10.57 grams of distilled water was then charged to the vessel and the contents were agitated until contents cleared in approximately 5.5 hours. The contents of the vessel were then cooled to 60 C., 103.21 grams KOH flake (100%) was then slowly charged to the vessel at a rate that allowed the batch temperature to be maintained at 60-80 C. and mixed until completely dissolved. It was then mixed an additional hour. After one hour, an FTIR scan was run to determine if the presence of ester had been eliminated. The mixture was sampled every 30 minutes until traces of esters had been eliminated. After the ester peak was eliminated, the batch was cooled to 40 C. and then placed under high shear agitation by using rotor stator mixer while maintaining the batch temperature at less than 80 C. by using an ice bath and by slowly increasing the RPM's of the mixer to 10,000 over a 1 hour time period. After the high shear mixing, 233.66 grams of ethylene glycol were charged and the resulting mixture was mixed for 30 minutes. The mix was cooled to <40 C. and then packaged off in an appropriate container.

EXAMPLE 18

(18) 128.46 grams of ethylene glycol, 62.06 grams of L-aspartic acid and 0.99 grams of phosphoric acid/85% were charged to a vessel, then placed under strong agitation and heated to 150 C. After 5 hours no particles were observed and 16.22 grams of distillate were collected. The batch was cooled to 120 C. and 7.67 grams of zinc oxide was slowly charged and dispersed with 15 minutes if agitation. 1.70 grams of distilled water was then charged to the vessel and the contents were agitated until the contents cleared in approximately 8.5 hours. The contents of the vessel were then cooled to 60 C., 14.27 grams KOH flake (100%) was then slowly charged to the vessel at a rate that allowed the batch temperature to be maintained at 60-80 C. and mixed until completely dissolved. It was then mixed an additional hour. After one hour, an FTIR scan was run to determine if the presence of ester had been eliminated. The mixture was sampled every 30 minutes until traces of esters had been eliminated. After the ester peak was eliminated, the batch was then cooled to <40 C. and then packaged off in an appropriate container.

EXAMPLE 19

(19) 333.9 grams of DMSO were charged to a reactor, placed under agitation and then 477 grams of sorbitol/70% were charged to the reactor. The mixture was then heated to 75 C. and placed under 20 mm of vacuum to strip out residual water. Once the formation of distillate ceased, the mixture was cooled to 40 C. and 611.59 grams of DMSO/sorbitol were recovered. In a mixing vessel, 71.3 grams of Example #5 were charged followed by 31.1 grams of the DMSO/sorbitol mixture and 31.1 grams of DMSO. The combination was mixed for 15 minutes and then 16.5 grams of KOH flakes were slowly charged holding the temperature below 80 C. The product was cooled below 40 C. and packaged.

EXAMPLE 20

(20) In a reactor, 122.24 grams of L-aspartic acid and 76.77 grams of propylene glycol were charged, placed under agitation and heated to 170 C. It was held at 17 C. until all particles disappeared. 199.04 grams of PG and 14.92 grams of zinc oxide were charged to the reactor while maintaining the batch temperature at 120-160 C. After batch appearance transitioned from milky to translucent, the batch was cooled to 40 C. and 61.81 grams of KOH/45% were slowly charged to reactor while maintaining the batch temperature below 80 C. The product was mixed 14 hours at 80 C. to saponify all ester linkages. The batch was then cooled to less than 40 C. and packaged

EXAMPLE 21

(21) In a reactor, charge 450.77 grams glycerin and 300 grams polysuccinimide (3000-5000 molecular weight) and heat to 140 C. and hold until all particles have reacted/dissolved. Cool to 40 C.

EXAMPLE 22

(22) In a mixing vessel under agitation, 48.8 grams of Example 21 and 28.6 grams of glycerin were charged. Then 22.6 grams of KOH/45% were slowly charged holding temp less than 80 C. during charge. After charging KOH, hold at 80 C. until ester linkages have been saponified. Cool to less than 40 C. and package off.

EXAMPLE 23

(23) In a mixing vessel under agitation, charge 48.8 grams of Example 22 and 28.6 grams of propylene glycol. Slowly charge 22.6 grams of KOH/45% holding temp less than 80 C. during charge. After charging KOH, hold at 80 C. until ester linkages have been saponified. Cool to less than 40 C. and package off.

EXAMPLE 24

(24) 60.55 grams of ethylene glycol, 130.01 grams of L-aspartic acid (ethylene glycol/aspartic acid molar ratio of 1:1 and a weight ratio of 32% to 68%) and 0.95 grams of phosphoric acid/85% were charged to a vessel, then placed under very low agitation and then slowly heated to 170 C. over a period of five hours. The rate of temperature rise was dependent on ability to increase agitation speed as high as product solids and viscosity would allow so as to not allow the product to burn. After 5 hours no particles were observed and 37.33 grams of distillate were collected. 279.42 grams of ethylene glycol were charged and the batch was cooled to 60 C. 49.82 grams KOH flake (100%) was then slowly charged to the vessel at a rate that allowed the batch temperature to be maintained at 60-80 C. and mixed until completely dissolved. It was then mixed and heated to 80 C and held an additional hour. The mix was cooled to <40 C. and then packaged off in an appropriate container.

EXAMPLE 25

(25) 48.4 grams of ethylene glycol were charge to a reactor, placed under agitation and a nitrogen sparge and heated to 90 C. 113.7 grams of a polysuccinimide (molecular weight 3000-5000) were slowly added to the reactor while increasing the agitation as needed and holding the temperature between 80 and 100 C. The very viscous product was then heated to 120 C. and 37.9 grams of addition polysuccinimide (molecular weight 3000-5000) were slowly charged to the reactor raising the molar ratio of PSI to Ethylene Glycol to 1:0.5 and the weight ratio 75.8% to 24.2%. The agitation was increased as product viscosity allowed. After 30 minutes the batch temperature was increased to 150 C. After 60 minutes at 150 C., all particles were dissolved. 384.48 grams of ethylene glycol were charged and the batch was cooled to 60 C. 63.46 grams of KOH (100%) were slowly charged to the reactor while maintaining the batch temperature 60-80 C. utilizing a cooling bath to assist in removing the heat from the exothermic neutralization. After all the KOH had been charged and was dissolved, the batch temperature was held at 80 C. under strong agitation for 3 hours. The batch was then cooled to <40 C and packaged off in an appropriate container.

EXAMPLE 26

(26) A dye was required in order to determine effectiveness of coating grams of each Example was placed under agitation and 0.4 grams of a 20% FD&C Blue #1 in a solvent was added to the 20 grams of each example. Each example was mixed for 15 minutes after addition of dye. Included in the testing were two aqueous commercial products,

(27) Avail & P-Max

Sample ID Prepared for Coating Test

(28) TABLE-US-00001 Example Sample ID ID Example 2 Sample 1 Example 3 Sample 2 Example 4 Sample 3 Example 6 Sample 4 Example 7 Sample 5 Example 8 Sample 6 Example 9 Sample 7 Example 10 Sample 8 Example 11 Sample 9 Example 12 Sample 10 Example 13 Sample 11 Example 14 Sample 12 Example 15 Sample 13 Example 16 Sample 14 Example 17 Sample 15 Example 18 Sample 16 Example 19 Sample 17 Example 20 Sample 18 Avail Sample 19 P-Max Sample 20 Example 23 Sample 21 Example 24 Sample 22 Example 25 Sample 23

EXAMPLE 27

(29) 200 grams of a technical grade of DAP was charged to a glass 1000 ml beaker. The beaker was then placed under an overhead agitator with an anchor agitator blade. The height of the beaker was adjusted such that the bottom of the anchor agitator blade was close to the bottom of the glass beaker. The RPM of the overhead stirrer was adjusted to 200 RPM's and the DAP was agitated for 30 seconds. After 30 seconds, a 2.0 gram of a sample of Example 21 was charged within 10 seconds. A stopwatch was used for timing to complete coating. (Visually: when 95% of DAP particles were colored blue). This was repeated for each of the tested samples from Example 26.

(30) After coating, the 200 grams of coated DAP was poured in a one quart jar and 200 grams of weight were placed on top of each sample in the quart jar. After setting for 48 hours, the weight was removed and a lid was placed on each quart jar. Each jar was then inverted and rated for flowability. If the contents of a jar did not flow in 5 minutes, a wooden handle of a 4 inch spatula was used to tap the jar to encourage flow. Flow rating is as follows:

(31) TABLE-US-00002 Rating Action after inversion 1 Instant flow 2 >70% flow in 1 minute 3 >70% flow in 1-3 minutes 4 >70% flow in 3-5 minutes 5 >70% flow after 1-2 taps 6 >70% flow after 3-4 taps 7 >70% flow after 5-6 taps 8 40-60% flow after 5-6 taps 9 20-40% flow after 5-6 taps 10 0-20% flow after 5-6 taps

Sample Performance on DAP

(32) TABLE-US-00003 Sample Time to coat 48 hour ID in seconds pack test Sample 1 20 4 Sample 2 24 5 Sample 3 20 3 Sample 4 15 2 Sample 5 27 3 Sample 6 26 4 Sample 7 18 3 Sample 8 14 2 Sample 9 27 3 Sample 10 34 5 Sample 11 32 4 Sample 12 25 4 Sample 13 24 4 Sample 14 24 4 Sample 15 27 3 Sample 16 29 5 Sample 17 30 6 Sample 18 21 2 Sample 19* 51 10 Sample 20* 56 10 Sample 21 32 4 Sample 22 28 4 Sample 23 28 4 *Difficult to determine coating time as the color was streaky and not continuous.

EXAMPLE 27

(33) 200 grams of a technical grade of magnesium sulfate was charged to a glass 1000 ml beaker. The beaker was then placed under an overhead agitator with an anchor agitator blade. The height of the beaker was adjusted such that the bottom of the anchor agitator blade was close to the bottom of the glass beaker. The RPM of the overhead stirrer was adjusted to 200 RPM's and the magnesium sulfate was agitated for 30 seconds. After 30 seconds, a 2.0 gram of a sample of Example 21 was charged within 10 seconds. A stopwatch was used for timing to complete coating. (Visually: when 95% of magnesium sulfate particles were colored blue).

(34) This was repeated for each of samples tested.

(35) After coating, the 200 grams of coated magnesium sulfate was poured in a one quart jar and 200 grams of weight were placed on top of each sample in the quart jar. After setting for 48 hours, the weight was removed and a lid was placed on each quart jar. Each jar was then inverted and rated for flowability. If the contents of a jar did not flow in 5 minutes, a wooden handle of a 4 inch spatula was used to tap the jar to encourage flow. Flow rating is as follows:

(36) TABLE-US-00004 Rating Action after inversion 1 Instant flow 2 >70% flow in 1 minute 3 >70% flow in 1-3 minutes 4 >70% flow in 3-5 minutes 5 >70% flow after 1-2 taps 6 >70% flow after 3-4 taps 7 >70% flow after 5-6 taps 8 40-60% flow after 5-6 taps 9 20-40% flow after 5-6 taps 10 0-20% flow after 5-6 taps

Sample Performance on Magnesium Sulfate

(37) TABLE-US-00005 Sample Time to coat in 48 hour ID seconds pack test Sample 1 22 4 Sample 2 23 5 Sample 3 20 4 Sample 4 18 2 Sample 5 27 3 Sample 6 29 3 Sample 7 17 3 Sample 8 14 2 Sample 9 29 3 Sample 10 31 6 Sample 11 33 4 Sample 12 26 4 Sample 13 36 4 Sample 14 25 5 Sample 15 28 3 Sample 16 29 5 Sample 17 30 6 Sample 18 18 2 Sample 19* 54 10 Sample 20* 58 10 Sample 21 33 4 Sample 22 28 3 Sample 23 28 3 *Difficult to determine coating time as the color was streaky and not continuous.

EXAMPLE 28

(38) 120 grams of prilled urea, 20 grams of fertilizer grade potassium sulfate, 40 grams of fertilizer grade diammonium phosphate, 10 grams of fertilizer grade zinc sulfate and 10 grams of fertilizer grade iron sulfate were charged to a glass 1000 ml beaker. The beaker was then placed under an overhead agitator with an anchor agitator blade. The height of the beaker was adjusted such that the bottom of the anchor agitator blade was close to the bottom of the glass beaker. The RPM of the overhead stirrer was adjusted to 200 RPM's and the contents of the compounded fertilizer were agitated for 30 seconds. After 30 seconds, a 2.0 gram of each sample to be tested was charged within 10 seconds. A stopwatch was used for timing to complete coating. (Visually: when 95% of magnesium sulfate particles were colored blue). This was repeated for each of the samples to be tested.

(39) After coating, the 200 grams of coated compounded fertilizer was poured in a one quart jar and 200 grams of weight were placed on top of each sample in the quart jar. After setting for 48 hours, the weight was removed and a lid was placed on each quart jar. Each jar was then inverted and rated for flowability. If the contents of ajar did not flow in 5 minutes, a wooden handle of a 4 inch spatula was used to tap the jar to encourage flow. Flow rating is as follows:

(40) TABLE-US-00006 Sample Time to cost 48 hour ID in seconds pack test Sample 1 18 3 Sample 2 22 5 Sample 3 23 3 Sample 4 14 2 Sample 5 26 3 Sample 6 28 5 Sample 7 20 3 Sample 8 18 2 Sample 9 25 3 Sample 10 32 5 Sample 11 28 4 Sample 12 25 4 Sample 13 26 3 Sample 14 27 4 Sample 15 27 3 Sample 16 28 5 Sample 17 28 6 Sample 18 15 2 Sample 19* 47 8 Sample 20* 48 9 Sample 21 29 5 Sample 22 28 4 Sample 23 29 5 *Difficult to determine coating time as the color was streaky and not continuous

(41) TABLE-US-00007 Rating Action after inversion 1 Instant flow 2 >70% flow in 1 minute 3 >70% flow in 1-3 minutes 4 >70% flow in 3-5 minutes 5 >70% flow after 1-2 taps 6 >70% flow after 3-4 taps 7 >70% flow after 5-6 taps 8 40-60% flow after 5-6 taps 9 20-40% flow after 5-6 taps 10 0-20% flow after 5-6 taps

EXAMPLE 29

(42) 100 grams of uncoated tall fescue grass seeds was charged to a glass 1000 ml beaker. The beaker was then placed under an overhead agitator with an anchor agitator blade. The height of the beaker was adjusted such that the bottom of the anchor agitator blade was close to the bottom of the glass beaker. The RPM of the overhead stirrer was adjusted to 100 RPM's and the seeds were agitated for 30 seconds. After 30 seconds, a 2.0 gram of a sample was charged within 10 seconds. The seeds were agitated until 95% of the seeds were coated.

(43) After coating, the 1 gram of coated seeds was added to 150 ml glass beaker in a manner to insure the seeds were equally distributed on the bottom of the beaker. The top of the beaker was sealed with a plastic wrap and placed in an dark environment at 30 C. The beaker was checked at 7, 14 and 21 days for signs of germination and rated for % of seeds that germinated.

(44) After 60 days, the plastic wrap covering was slit and a prepared Contec test strip was inserted and placed just above the seed to test for presence of mold and mildew.

(45) TABLE-US-00008 % germination Rating of seeds 0 None 1 0-5% 2 5-10% 3 10-20% 4 20-30% 5 >30%

Sample Performance of Tall Fescue Grass Seed

(46) TABLE-US-00009 Sample Mold/mildew ID 7 days 14 days 21 days after 60 days Sample 1 0 0 0 No Sample 2 0 0 0 No Sample 3 0 0 0 No Sample 4 0 0 0 No Sample 7 0 0 0 No Sample 8 0 0 0 No Sample 9 0 0 0 No Sample 10 0 0 0 No Sample 14 0 0 0 No Sample 18 0 0 0 No Sample 19 0 1 2 Yes Sample 20 0 1 2 Yes

(47) The below table 1 summarizes the compositions that occur in each of the examples. The presence of an X in table 1 means that the particular example composition contains that particular component.

(48) TABLE-US-00010 TABLE 1 Example No. DMSO Glycerin TPGME Sorbitol DMG PG DPG EG PC TT DD AT DMA 1 X 2 X X 3 X X 4 X X 5 X 6 X 7 X X 8 X X 9 X 10 X 11 X 12 X 13 X 14 X X X 15 X 16 X 17 X 18 X 19 X X 20 X 21 X 22 X 23 X X 24 X 25 X DMSOdimethylsulfoxide PGpropylene glycol DPGdipropylene glycol DMGDimethyl Gluterate TPGMEtripropylene glycol methyl ether EGethylene glycol

(49) Samples from Examples 1-25 were evaluated for safety and environmental properties and the results are shown in the below Table 2:

(50) TABLE-US-00011 TABLE 2 Aquatic Sample Human Health Flash Toxicity # Rating Point F. Rating Ex 1 1.0 >145 Low Ex 2 1.0 >145 Low Ex 3 1.0 >145 Low Ex 4 1.0 >145 Low Ex 5 1.0 >145 Low Ex 6 1.0 >145 Low Ex 7 1.0 >145 Low Ex 8 1.0 >145 Low Ex 9 1.0 >145 Low Ex 10 1.0 >145 Low Ex 11 1.0 >145 Low Ex 12 1.0 >145 Low Ex 13 1.0 >145 Low Ex 14 1.0 >145 Low Ex 15 1.0 >145 Low Ex 16 1.0 >145 Low Ex 17 1.0 >145 Low Ex 18 1.0 >145 Low Ex 19 1.0 <145 Low Ex 20 1.0 >145 Low Ex 21 1.0 >145 Low Ex 22 1.0 >145 Low Ex 23 1.0 >145 Low Ex 24 1.0 >145 Low Ex 25 1.0 >145 Low

(51) The Human Health rating is based on HMIS (Hazardous Materials Information System) rating on Health of any organo solvent component >2%

(52) The Flash Point is based on flash point of any organo solvent component >5%

(53) The Aquatic Toxicity Rating is based on any organo solvent component at any level

(54) The following references are incorporated by reference in their entireties.

(55) TABLE-US-00012 4,839,461 Boehmke 4,172,072 Ashmead 4,799,953 Danzig 4,813,997 Kinnersley 4,863,506 Young 5,059,241 Young 5,047,078 Gill 5,350,735 Kinnersley 5,593,947 Kinnersley 5,783,523 Koskan 5,814,582 Koskan 6,753,395 Sanders 6,756,461 Sanders 6,818,039 Sanders 8,043,995 Sanders 8,016,907 Sanders 8,025,709 Sanders 5,994,265 Barclay 7,001,869 Johnson 6,557,298 Obert

(56) It is contemplated and therefore within the scope of the present invention that any feature that is described above can be combined with any other feature that is described above. When mixtures, formulations and/or compositions are discussed, it should be understood that those mixtures, formulations and/or compositions are contemplated as being parts of bigger mixtures, formulations and/or compositions. Further, if a composition is enumerated, methods using and methods of making that composition are contemplated and within the scope of the present invention. When a range is discussed, it is contemplated and therefore within the scope of the invention that any number that falls within that range is contemplated as an end point generating a plurality of sub-ranges within that range. For example if a range of 1-10 is given, 2, 3, 4, 5, 6, 7, 8, and 9 are contemplated as end points to generate a sub-range that fit within the scope of the enumerated range. Moreover, it should be understood that the present invention contemplates minor modifications that can be made to the compositions and methods of the present invention. In any event, the present invention is defined by the below claims.