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

15) A method of making a liquid composition of biodegradable polymers and/or oligomers comprised of 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 aldehyde reactive groups, wherein the cyano containing nitrification inhibitors reactive groups are selected from the group consisting of a) primary and secondary amines, b) amides, c) thiols, d) hydroxyls and e) phenols, wherein the reaction possesses one or more of the following steps:

• a) charging the aldehyde(s), the cyano containing nitrification inhibitors, and NAPAOL to a reaction vessel by one or more steps selected from the group consisting of:
• i) charging said aldehydes, said cyano containing nitrification inhibitors and said NAPAOL to said reaction vessel and starting mixing
• ii) charging a mixture of said cyano containing nitrification inhibitors and said NAPAOL to said reaction vessel, starting mixing and heating the mixture to 40-90° C. holding the mixture for 0-60 minutes at temperature, cooling the mixture down to 20-60° C. and then charging said aldehyde,
• iii) charging a mixture of said cyano containing nitrification inhibitors and said NAPAOL to the reaction vessel, sparging the reaction vessel of oxygen and then charging said aldehyde,
• b) proceeding with a first reaction by one or more steps selected from the group consisting of:
• i) heating contents of the reaction vessel to 50-90° C. and holding at temperature for 1-4 hours,
• ii) heating contents of the reaction vessel to 70-80° C. and holding at temperature for 1-4 hours
• iii) heating contents of the reaction vessel to 50-90° C. and holding at temperature until contents are clear,
• iv) heating contents of the reaction vessel to 70-80° C. and holding at temperature until contents are clear,
• c) proceeding with a second reaction by one or more steps selected from the group consisting of:
• i) placing the reaction vessel under a vacuum of 0.5-50 mm Hg, increasing temperature to 90-120° C. and holding under vacuum and at temperature until an aldehyde content is 0-700 ppm,
• ii) cooling contents of the reaction vessel to 20-60° C., charging the reaction vessel with one or more acid catalysts selected from the group consisting of methane sulfonic acid, sulfuric acid, para-toluene sulfonic acid, phosphoric acid, and methane phosphonic acid, placing the reaction vessel under a vacuum of 0.5-50 mm Hg, increasing temperature to 90-120° C. and holding under vacuum and at temperature until the aldehyde content is 0-700 ppm,
• d) terminating the reaction by one or more steps selected from the group consisting of:
• i) breaking vacuum with hard sparging the reaction vessel with an inert gas to assist in removing residual aldehyde,
• ii) ensuring formaldehyde is <700 ppm,
• iii) cooling contents below 40° C.,
• iv) charging the reaction vessel with one or more acid catalyst neutralizing agents selected from the group consisting of NaOH, NaOCH3, Na2CO3, KOH, K2CO3, NH3 and one or more alkanolamines selected from the group represented by the structure:
• wherein R5 is:
• C2H4OR8 or C3H6OH
• wherein R6 is:
• H, C2H4OR8 or C3H6OH
• wherein R7 is:
• H, C2H4OR8 or C3H6OH
• wherein R8 is:
• (C2H4O)gH
• and g is an integer between 1-10
• wherein said 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:
• R9S(O)xR10
• wherein R9 and R10 are each independently a C1-6alkylene group, an aryl group, or C1-3alkylenearyl group or R9 and R10 together with the sulfur to which they are attached form a 4 to 8 membered ring wherein R9 and R10 together are a C1-6alkylene 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) and 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 and one or more trialkylphosphates represented by the formula:
• wherein:
• R22 is an alkyl radical —C1H3 to —C6H13
• R23 is an alkyl radical —C1H3 to —C6H13
• R24 is an alkyl radical —C1H3 to —C6H13
• f) 1,2-dimethyloxyethane, g) 2-methoxyethyl ether and h) cyclohexylpyrrolidone,
• wherein said aldehyde(s) utilized as a reactant to produce said biodegradable polymers and /or oligomers comprise the structure:
• wherein Q is:
• O, S
• wherein R11 is:
• —H, an alkyl radical —C1H3 to —C6H13, —CH═CH2, —C4H3O, —C6H5, —C6H11, CHO, C2H3O, C3H5O, C4H7O, C7H5O or —R12O2R13,
• wherein R12 is:
• —C, —C2H2, —C3H4, —C4H6, —C5H8, —C6H10
• wherein R13 is:
• —H, CH3, C2H3, C3H7, C4H9
• and wherein said cyano containing nitrification inhibitors utilized as a reactant to produce said biodegradable polymers and/or oligomers comprises one or more members selected from the group consisting of:

19) A composition comprising biodegradable polymers and/or oligomers wherein said biodegradable polymers and/or oligomers are made by using a non-aqueous polar, aprotic organic liquid, NAPAOL, as a reaction medium for a reaction of aldehyde(s) with one or more cyano containing nitrification inhibitors that have one or more reactive groups that react with the aldehyde(s) to generate the composition 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:
• R9S(O)xR10
• wherein R9 and R10 are each independently a C1-6alkylene group, an aryl group, or C1-3alkylenearyl group or R9 and R10 together with the sulfur to which they are attached form a 4 to 8 membered ring wherein R9 and R10 together are a C1-6alkylene 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:
• R22 is an alkyl radical —C1H3 to —C6H13
• R23 is an alkyl radical —C1H3 to —C6H13
• R24 is an alkyl radical —C1H3 to —C6H13
• g)1,2-dimethyloxyethane, h) 2-methoxyethyl ether, and i) cyclohexylpyrrolidone.