Process to conserve cyano-function and improve performance of low molecular weight nitrification inhibitors to improve fertilizer efficiency

Patent metadata

Field	Value
Publication number	US-10273194-B2
Application number	US-201715854319-A
Country	US
Kind code	B2
Filing date	Dec 26, 2017
Priority date	Jul 4, 2016
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

Abstract

Disclosed are compositions and methods of making a liquid fertilizer additive of biodegradable polymers and/or oligomers comprised of utilizing a non-aqueous polar, aprotic organo liquid (NAPAOL) as the reaction medium for the reaction of aldehyde(s) with cyano-containing nitrification inhibitors that have one or more groups that react with the aldehyde(s) wherein said reactive groups are selected from the group consisting of a) primary and secondary amines, b) amides, c) thiols, d) hydroxyls and e) phenol.

First claim

We claim:

1. A method of making a liquid composition of biodegradable polymers and/or oligomers comprising utilizing a non-aqueous polar, aprotic organic liquid, NAPAOL, as a reaction medium for a reaction of aldehyde(s) with cyano containing nitrification inhibitors that have one or more reactive groups that react with the aldehyde(s) to generate a reaction product wherein said one or more reactive groups are selected from the group consisting of a) primary and secondary amines, b) amides, c) thiols, d) hydroxyls and e) phenols, wherein reaction parameters are implemented to limit the presence of water throughout the reaction, minimize a temperature of any acid catalyst addition, and to minimize reaction time and temperature to conserve a cyano function of the nitrification inhibitors, wherein the NAPAOL comprises one or more members selected from the group consisting of:
a) dimethyl sulfoxide,
b) dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:
R 9 S(O) x R 10
wherein R 9 and R 10 are each independently a C 1-6 alkylene group, an aryl group, or C 1-3 alkylenearyl group or R 9 and R 10 together with the sulfur to which they are attached form a 4 to 8 membered ring wherein R 9 and R 10 together are a C 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

c) one or more alkylene carbonates selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate d) 1-Methyl-2-pyrrolidone, e) one or more organo phosphorous liquids selected from the group consisting of hexamethylphosphoramide, f) one or more trialkylphosphates represented by the formula:

wherein:
R 22 is an alkyl radical —C 1 H 3 to —C 6 H 13
R 23 is an alkyl radical —C 1 H 3 to —C 6 H 13
R 24 is an alkyl radical —C 1 H 3 to —C 6 H 13

g) 1,2-dimethyloxyethane, h) 2-methoxyethyl ether, and i) cyclohexylpyrrolidone,

wherein the composition further comprises one or more organo polyorganic acids and/or their salts, wherein the organo polyorganic acids and/or their salts is a monomer homopolymer, a copolymer and/or a terpolymer of one or more members selected from the group consisting of:
aspartic acid
glutamic acid
maleic anhydride
itaconic anhydride
citraconic anhydride
citric acid; and
acrylic acid;

wherein the organo polyorganic acids are present in an amount that is about 5-50% of a total composition and wherein a cation of salts of the polyacids comprises one or more members selected from the group consisting of one or more metals and organoamines wherein the one or more metals are selected from the group consisting of Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, and Ni and the one or more organoamines are selected from the group consisting of mono C 1-6 amine, di C 1-6 amine, tri C 1-6 amine, mono ethanol amine, diethanol amine, triethanol amine, monoisopropyl amine, diisopropyl amine, triisopropyl amine, and diethyl amine.

2. The method of claim 1 , wherein aldehydes utilized as a reactant to produce said biodegradable polymers and/or oligomers comprise one or more members selected from the group consisting of the structure:

wherein Q is: O, or S,
wherein R 11 is: —H, an alkyl radical —C 1 H 3 to —C 6 H 13 , —CH═CH 2 , —C 4 H 3 O, —C 7 H 7 , —C 6 H 5 , —C 6 H 11 , CHO, C 2 H 3 O, C 3 H 5 O, C 4 H 7 O, C 7 H 5 O or —R 12 O 2 R 13 ,
wherein R 12 is: —C, —C 2 H 2 , —C 3 H 4 , —C 4 H 6 , —C 5 H 8 , —C 6 H 10
wherein R 13 is: —H, CH 3 , C 2 H 3 , C 3 H 7 , C 4 H 9 .

3. The method of claim 1 , wherein the cyano containing nitrification inhibitors utilized as a reactant to produce said biodegradable polymers and/or oligomers comprise one or more of the following:

4. The method of claim 1 , wherein said cyano containing nitrification inhibitors and said aldehydes utilized as reactants to produce said biodegradable polymers and/or oligomers comprise a molar ratio of cyano containing nitrification inhibitors' aldehyde reactive functionalities to aldehyde compounds of 1:1, resulting in a composition wherein at least 90% of the total nitrification inhibitor content is a polymeric/oligomeric compound.

5. The method of claim 1 , wherein said cyano containing nitrification inhibitors and said aldehydes utilized as reactants to produce said biodegradable polymers and/or oligomers comprise a molar ratio of cyano containing nitrification inhibitors' aldehyde reactive functionalities to aldehyde compounds of 1:1 to 2:1 wherein the reaction results in a composition at least 70% of the total nitrification inhibitor content is a polymeric compound.

6. The method of claim 1 , wherein said cyano containing nitrification inhibitors and said aldehydes utilized as reactants to produce said biodegradable polymers and/or oligomers comprise a molar ratio of cyano containing nitrification inhibitors aldehyde reactive functionalities to aldehyde compounds of 2:1 to 4:1 wherein the reaction results in a composition wherein at least 51% of the total nitrification inhibitors content is polymeric/oligomeric compounds.

7. The method of claim 1 wherein the cyano containing nitrification inhibitor reactant utilized to produce biodegradable polymers and/or oligomers comprises dicyandiamide.

8. The method of claim 1 wherein the aldehyde utilized to produce biodegradable polymers and/or oligomers comprises one or more members selected from the group consisting of paraformaldehyde and formaldehyde.

9. The method of claim 1 wherein the NAPAOL utilized as the reaction medium to produce biodegradable polymers and oligomers comprises dimethyl sulfoxide.

10. The method of claim 1 wherein said liquid composition of biodegradable polymers and/or oligomers possesses one or more of the following properties selected from the group consisting of:
a) yields better control over polymer distribution,
b) yields products with lower water solubility resulting in slower dissolution of nitrogen sources and added biologically active agents and biologics once applied to the soil,
c) yields products that slow the loss of nitrification inhibition by reducing the nitrification inhibitors' volatility, limiting migration through the soil by increasing a molecular weight of the product which lowers the nitrification inhibitors' water solubility,
d) yields products that extend the nitrification inhibitors' lifespan by incorporation into a polymer backbone, which when biodegradation occurs results in a slow release of incorporated nitrification inhibitors,
e) yields products that retain some nitrification inhibition capability through formation of methylene bis nitrification inhibitor oligomers based on the reaction product of a ratio of 2 moles of one or more nitrification inhibitors that contain 1 to 2 aldehyde reactive groups reacted with one mole of aldehyde,
f) yields products with lower viscosity relative to polymers formed in an aqueous medium which aides in coating solid nitrogen sources,
g) yields products that are able to maintain said biodegradable polymers at levels of 20-80% in a NAPAOL,
h) yields products that are able to provide improved and even delivery of the liquid composition to a surface of fertilizer granules and solid nitrogen sources of said biodegradable polymers/oligomers while not causing clumping of the fertilizer gra

Assignees

• Mcknight Gary David
• Rayburn Randall Linwood
• Xu Wei

Inventors

• Mcknight Gary David
• Rayburn Randall Linwood
• Xu Wei

Classifications

• G01J3/42

  Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry (beam switching arrangements G01J3/08) · CPC title

• C08L2201/06

  Biodegradable · CPC title

• C08G12/28

  with substituted diazines, diazoles or triazoles · CPC title

• C05C11/00 Primary

  Other nitrogenous fertilisers · CPC title

• C07C255/24

  containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton · CPC title