NZ626377B2 - Solvent systems of n-alkyl thiophosphoric triamides and methods of use in agricultural applications - Google Patents

Abstract

Disclosed herein are dioxolane compound based solvent system compositions for the formulation of alkyl thiophosphoric triamide urease inhibitors, that provide stable dispersion of alkyl thiophosphoric triamides for even distribution (in low or high concentrations) onto fertilizers containing urea in liquid or solid form. liquid or solid form.

Description

SOLVENT SYSTEMS OF N-ALKYL THIOPHOSPHORIC TRIAMIDES AND S OF USE IN AGRICULTURAL APPLICATIONS CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit Of US. Provisional Application Serial NO. 61/630,456, filed on December 12, 2011, herein incorporated by reference. NZ 723492 is a divisional out Of the t application. The ption Of the present ion and the invention Of NZ 723492 iS retained herein for clarity and completeness.

FIELD OF THE INVENTION This invention s to compositions and methods for use Of solvent systems containing alkyl thiophosphoric triamides, used to facilitate oration Of the alkyl thiophosphoric triamides into solid state or liquid state fertilizer formulations.

BACKGROUND OF THE INVENTION In the current agrochemical market, farmers use various fertilizers to impart macronutrients to plants either by application tO the SOil or application to plant leaves.

Nitrogen, phosphorus, potassium, calcium, magnesium, and sulfur are the six macronutrients that must be supplied to the plants and soil manually by farmers. In many crops, the amount Of en supplied is critical to the overall quality and growth Of the crop. Nitrogen is supplied in either urea or ammonium phosphate forms. Due to the high water solubility Of these salts, however, much Of the nitrogen applied is lost tO run—Off and leaching. In ammonium-based products, if the nitrogen iS not lost tO leaching or run-Off, it is being converted to a gas by an enzyme called urease where the ammonia can bind to soil les. Conversion occurring near the surface Of the soil, however, does not allow for binding and this ammonia is lost tO the atmosphere. Urease inhibitors are used to protect a farmer’s investment in fertilizers by preventing the breakdown Of urea by , the soil microbe responsible for converting PCT/U82012/069080 urea to usable ammonia in the soil. This increases the amount of time the en remains'in the soii and is available to the plant for absorption.

SUMMARY OF THE INVENTION Urease inhibitors can be used with a fertilizer (i.e., incorporated into a urea- containing fertilizer) to slow the conversion of ammonium ions to ammonia gas and thus slow the lost of ammonia to volatilization, thus making it available to plants in the soil longer. increasing the amount of time that the nitrogen is available to the plant ses the effectiveness of the fertilizer which positivety impacts crop yield and quality. Fertilizers, in one embodiment, are common water soluble inorganic fertilizers that provide nutrients such as phosphorus-based, nitrogen-based, potassium—based or sulphur—based fertilizers. es of such fertilizers e: for nitrogen as the nutrient: nitrates and or ammonium salts such as ammonium nitrate, including in ation with urea e.g. as Uram type materials, calcium um nitrate, ammonium suphate nitrate, ammonium phosphates, ularly mono—ammonium phosphate, di-ammonium phosphate and ammonium osphate, ammonium sulphate, and the less commonly used calcium nitrate, sodium nitrate, potassium nitrate and ammonium chloride. it is understood that a fertilizer ition can comprise one or a combination of the izers described herein.

A typical urease inhibitor, NBPT (N—(n—butyl)—thiophosphoric triamide), however, faces drawbacks in its use as NBPT is extremely difficult to handle. NBPT is a sticky, waxy, heat and water sensitive materiai, which cannot be used in its solid form, as it is used at low concentrations making it difficult to evenly distribute on urea prills (is, large granuies) and in soil. in order to evenly distribute the NBPT onto the urea, the NBPT should be dispersed into a carrier prior to being sprayed onto the urea. Thus, the use of a solvent system containing the NBPT is desirable as, in its liquid form, the solvent system is capable of distributing the NBPT into ar urea (e.g., urea prills) and into liquid fertilizers containing urea. ~By introducing the NBPT to liquid fertilizers containing urea (for example, urea-ammonium nitrate solutions or UAN) in a solvent system, the NBPT is capable of being better dispersed in the liquid fertilizer. [0007} Thus, it is desirable to have a low cost solvent system ning alkyl thiophosphoric triamide, and in particular, (N-(n-butyl)-thiophosphortctriamide), that has a favorable toxicological and/or ecological profile and ble characteristics in terms of low lity, biodegradability or ready biodegradability (i.e., readily biodegradable), low toxicity or low hazard level.

The present invention described herein will become nt from the following detailed description and examples, which comprises in one aspect, are formulations comprising a mixture or solution of at least one alkyl thiophosphoric triamide (from about 15% to 35% by weight of formulation) in at least one solvent selected from: at least one c ester (from about 5% to 35% by weight of formulation), at least one dioxolane (from about 25% to 70% by weight of formulation), at least one ester-amide or diamide (from about 10% to 50% by weight of formulation), at least one alkyldimethylamide (from about 10% to 50% by weight of ation), at least one alkyl lactate (from about 0% to 60% by weight of formulation), ethyl levulinate (from about 0% to 60% by weight of ation), at least one glycerine or glycerine derivative (from about 0% to 75% by weight of formulation), at least one alkylene carbonate (from about 0% to 60% by weight of formulation), at least one alkyoxyalcohol, PCT/U82012/069080 ether alcohol, dialkyl alcoholamine (for exampie, dimethyl ethanolamine, diethyl ethanolamine), amine alcohol, amino alcohol or alcohol (from about 0% to 75% by weight of formulation), or any combination thereof. {0009] In another aspect, described herein are ations comprising a mixture or solution of at least one alkyl thiophosphoric triamide in at least one solvent selected from the group ting of: t a) at least one dibasic ester; [00111 b) at least one dioxolane compound of a (la): CHZJiOHn o O R8 7 (la) WO 2013l’090324 2012/069080 n R5 and R7 individually comprises a hydrogen, an alkyl group, an alkenyl group, a phenyl group, wherein n is an integer of from 1 to 10; {0013] c) at least one ester—amide 0r diamide, which in one embodiment, is at least one nd of formula (Ila): {0014] Rgooc-A-CONR4R5 (Ila), {0016] wherein R3 comprises a C1635 alkyl group; wherein R4 and R5 individually se a C1—C36 alkyl group, wherein R4 and R5 can optionally together form a ring; and wherein A is a linear or branched divalent C2-Ce alkyl group; {0017] d) at least one alkyldimethylamide; {0018] e) at least one alkyl lactate; {0019] f) ethyl levulinate; g) xyethanol; {0021] h) at least one glycerine or glycerine derivative; l) propylene carbonate; and {0023] j) any combination thereof. {0024] In one embodiment, Regarding the formula li(a), R3 can be group chosen from, among others, saturated or unsaturated, linear or branched, optionally cyclic, optionally aromatic hydrocarbon—based groups comprising an average number of carbon atoms ranging from 1 to 36. in a further embodiment, R3 can is selected from the group consisting of a saturated C1-035 alkyl group, an unsaturated 01-035 alkyl group, a linear (31-035 alkyl group, a ed 01-035 alkyl group, a cyclic 01-635 alkyl group, and an aromatic C1-C36 alkyl group.

W0 2013f090324 PCT/U82012/069080 In another embodiment, R4and R5, which are identical or different, can be groups chosen from, among others, saturated or unsaturated, linear or branched, optionally cyclic, ally aromatic, ally substituted hydrocarbon-based groups comprising an average number ofcarbon atoms ranging from 1 to 36. A can be a linear or branched nt alkyl group comprising an average number of carbon atoms ranging from 2 to 12. in a further embodiment, R4 and R5 individually comprise a saturated 01—036 alkyl group, an unsaturated 014335 alkyl group, a linear C1~C35 alkyl group, a branched 01-035 alkyl group, a cyclic (31-036 alkyl group, or an aromatic (31—035 alkyl group. in one embodiment, aikyl thiophosphoric triamide is N-(n~butyl)— thiophosphoric triamide. The alkyi osphoric triamide can be present in the dispersion in an amount between about 0.5 % by weight of the dispersion and about 50 % by weight of the dispersion or, in another embodiment, can be present in the dispersion in an amount between about 1 % by weight of the dispersion and about 40 % by weight ofthe dispersion, and, in r embodiment, can be present in the sion in an amount between about 0.5 % by weight of the dispersion and about 20 % by weight of the dispersion. In one ular embodiment, the alkyl thiophosphoric triamide is present in the dispersion in an amount between about 1 % by weight of the dispersion and about 30 % by weight of the dispersion.

The at least one dibasic ester can comprises at least two of: dialkyl giutarate, dialkyl ethylsuccinate, dialkyl adipate, dialkyl succinate or dialkyl giutarate. In another embodiment, the at least one dibasic ester comprises a blend of dialkyl methylgiutarate, l ethylsuccinate and, optionally, dialkyl adipate. in a PCT/U52012/069080 further embodiment, the at least one dibasic ester comprises a blend of dialkyl adipate, dialkyl succinate and dialkyl glutarate. in one embodiment, the alkyl lactate is a straight pr branched alkyl lactate, in one embodiment, the alkyl lactate is a (31-03 alkyl lactate. In another embodiment, the alkyl e is a C1-C5 alkyl lactate.

In another aspect, bed herein are ations comprising a mixture or solution of at least one alkyi thiophosphoric triamide in at least one t selected from the group consisting of: a) at least one dibasic ester selected from dialkyl methylglutarate, diaikyl ethylsuccinate, dialkyl adipate, dialkyl succinate or dialkyl glutarate; b) at least one dioxolane compound of formula (la): [00323 Re R? (la) wherein R6 and R7 individually comprises a en, an alkyt group, an alkenyl group, a phenyl group, wherein n is an integer of from 1 to 10; c) at least one compound of a (lla): R300C—A-CONR4R5 (Ha) PCT/U$2012/069080 wherein R3 comprises 3 014335 alkyl groupiwherein R4 and R5 individually comprise a 01-035 alkyl group, wherein R4and R5 can optionally er form a ring; and wherein A is a linear or branched divalent 02-05 alkyl group; d) at least one alkyldimethylamide; e) at least one alkyl lactate; l) propylene carbonate; and j) any combination f.

In one embodiment, the alkyldimethylamide is N,N—Dimethyldodecylamide in one particular embodiment, the dibasio ester is a blend comprising: (i) a first c ester of formula: [00463 (5): (ii) a second dibaeio ester of formula: (ll), and (iii) optionally, a third dibasic ester of formula: (Ill), wherein R1 and R2 individually comprise a 01-08 alkyl group.

In another aspect, described herein are methods for preparing an ltural composition comprising contacting the formulation as defined herein with a urea-based fertilizer composition. In one embodiment, ased izer composition is in ar or prill form. In another embodiment, the urea-based fertilizer composition is in substantially liquid form.

ED DESCRIPTION As used herein, the term "alkyl" means a saturated straight chain, branched chain, or cyclic hydrocarbon radical, including but not limited to, methyl, ethyl, n-propyl, iso—propyl, n-butyl, sec-butyl, t-butyl, pentyl, n—hexyl, and cyclohexyl.

As used herein, the term "aryl" means a monovalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds, which may be substituted one or more of carbons of the ring with hydroxy, alkyl, alkenyl, halo, haloalkyl, or amino, including but not limited to, phenoxy, phenyl, methylphenyl, dimethylphenyl, hylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl, and tristyrylphenyl.

As used herein, the term "aikytene" means a divalent saturated straight or branched chain hydrocarbon radical, such as for e, methylene, dimethylene, hylene.

As used herein, the terminology "(CrCs)" in reference to an organic group, wherein r and s are each integers, indicates that the group may n from r carbon atoms to 3 carbon atoms per group.

As used herein, the terminology "surfactant” means a compound that when ved in an aqueous medium lowers the surface tension of the aqueous medium.

In one embodiment, the solvent system is chosen from one or more of the following components (a through 3'), below. In another embodiment, the solvent is chosen from at least one components, typically, two or more components. a) at least one dibasic ester; b) at least one dioxolane compound of formuta (la): CH2}—-OHn o O R5 7 (E3) “10- W0 20131090324 2012/069080 n R5 and R7 individually comprises a hydrogen, an alkyl group, an alkenyl group, a phenyl group, wherein n is an integer of from 1 to 10; c) at least one compound of formula (lla): R300C-A~CONR4R5 (Na), wherein R3 ses a (31-035 alkyl group; wherein R4 and R5 individually comprise a C1~C35 alkyl group, wherein R4 and R5 can optionally together form a ring; and wherein A is a linear or branched divalent Cz-Cs alkyl group; d) at least one alkyldimethylamide; e) at least one alkyl lactate; f) ethyl levulinate; g) 2—butoxyethanol; h) at least one glycerine or glycerine derivative; l) propylene carbonate; and j) any combination thereof. in one embodiment, a C1—C4 alcohol chosen from t—butyl alcohol, butyl l, iso—propyl alcohol, or propyl alcohol can be added to the solvent. In one typical embodiment, the C1—C4 l is opyl alcohol. in one embodiment, the solvent comprises (i) one or a (ii) blend of dibasic esters. in one embodiment, the blend comprises adducts of alcohol and linear diacids, the adducts having the formula R1-OOC-A-COO-R2 wherein R1 and/or R2 comprise, individually, a C1—C9 alkyl, more typically a 01—08 alkyl, and A comprises a e of — (CH2)4-, -(CH2)3, and —(CH2)2-t In another embodiment, R1 and/or R2 comprise, -11» WO 90324 PCT/U82012/069080 individually, a (34-012 alkyl, more lly a 04—08 alkyl. in one embodiment, R1 and R; can individually comprise a hydrocarbon group originating from fusel oil. In one embodiment, R1 and R2 individually can comprise a arbon group having 1 to 8 carbon atoms. in one embodiment, R1 and R2 individually can comprise a arbon group having 5 to 8 carbon atoms. in another embodiment, A comprises a least one, typically at least two, of: —(CH2)4—, —CH2CHZCH(CH3)-, -CH20H(C2H5)—, —(CH2)4—, — CHZCHZCH(CH3)~, or —CH20H(CZH5)-. in one embodiment, the blend comprises adducts of alcohol and branched or linear diacids, the s having the formula R1—OOC—A—COO-R2 wherein R1 and/or R2 comprise, individually, a (31—012 alkyl, more typically a Ci-Cg alkyi, and A comprises a mixture of —(CH2)4-, -CHZCH2CH(CH3)-, and (C2H5)-. in another embodiment, R1 and/or R2 comprise, individually, a 04—012 aikyi, moretypicaliy a 04-08 alkyl. it is understood that the acid portion may be derived from such dibasic acids such as adipic, succinic, glutaric, oxalic, malonic, pimelic, suberic and azelaic acids, as well as mixtures The c esters can be obtained by a process comprising an “esterification” stage by reaction of a diacid of formula HOOC-A—COOH or of a diester of formula MeOOC—A-COOMe with a branched alcohol or a mixture of alcohols. The reactions can be appropriately catalyzed. Use is preferably made of at least 2 molar ients of alcohols per diacid or diester. The reactions can, if appropriate, be promoted by extraction of the reaction by—products and followed by stages of filtration and/or of purification, for exampie by distillation.

PCT/U82012/069080 The s in the form of mixtures can in particular be obtained from a mixture of dinitrile compounds in particular produced and recovered in the process for the manufacture of adiponitrile by double hydrocyanation of butadiene. This s, used on a large scale industrially to produce the greater majority of the adiponitrile consumed worldwide, is described in numerous patents and works. The reaction for the hydrocyanation of butadiene results predominantly in the formulation of linear dinitrilee but also in formation of branched dinitriles, the two main ones of which are glutaronitrile and ethylsuccinonitrile. The branched dinitrile compounds are separated by distillation and red, for example, as top traction in adistillation column, in the stages for separation and purification of the adiponitrile. The branched iles can subsequently be converted to diacids or diesters (either to light diesters, for a uent transesterification reaction with the alcohol or the mixture of alcohols or the fusel oil, or ly to diesters in accordance with the invention).

Dibasic esters of the present invention may be derived from one or more by- products in the production of polyamide, for example, polyamide 6,6. ln one embodiment, the at least one dibasic ester comprises a blend of linear or branched, cyclic or noncyclic, 01—020 alkyl, aryl, alkylaryl or kyl esters of adipic diacids, glutaric diacids, and succinic diacids. in another embodiment, the composition ses a blend of linear or branched, cyclic or noncyclic; C1—Czo alkyl, aryl, alkylaryl or arylalkyl esters of adipic diacids, glutaric diacids! and ethylsuccinic diacids Generally, polyamide is a copolymer ed by a condensation reaction formed by reacting a diamine and a dicarboxylic acid. Specifically, polyamide 6,6 is a PCT/U82012/069080 copolymer prepared by a condensation on formed by reacting a diamine, typically hexamethylenediamine, with a oxylic acid, typically adipic acid. in one embodiment, the blend of dibasic esters can be derived from one or more by—products in the reaction, synthesis and/or production of adipic acid utilized in the production of polyamide, the composition comprising a blend of dialkyl esters of adipic diacids, glutaric s, and succinic diacids (herein referred to sometimes as “AGS” or the "AGS blend”). in one embodiment, the blend of esters is derived from by~products in the reaction, synthesis and/or production of hexamethylenediamine utilized in the production of poiyamide, typically poiyamide 6,6. The composition comprises a blend of dialkyl esters of adipic s, methylglutaric diacids, and ethylsuccinic diacids (herein referred to sometimes as “MGA”, “MGN”, “MGN blend” or “MGA blend”). in n ments, the dibasic ester blend comprises: a diester of formula I: (i) ; a diester of formula ll: W0 90324 PCT/U52012/069080 (ll) ; and a diester of formula lll: (ill).

R1 andlor R2 can individually comprise a arbon having from about 1 to about 8 carbon atoms, typically, methyl, ethyl, propyl, isoprOpyl, butyl. yl, n-butyl, isoamyl, hexyi, heptyl or octyl. In such embodiments, the blend typically comprises (by weight of the blend) (i) about 15% to about 35% of the diester of formula I, (ii) about 55% to about 70% of the diester of formula ll, and (iii) about 7% to about 20% of the diester of formula Ill, and more typically, (i) about 20% to about 28% of the diester of formula I, (ii) about 59% to about 67% of the diester of formula ll, and (iii) about 9% to about 17% of the diester of a III. The blend is generally characterized by a flash point of 98 ”C, a vapor pressure at 20 ”C of less than about 10 Pa, and a distillation temperature range of about 200—300 °C. in certain other embodiments, the dibasic ester blend comprises: a d iester of the formula IV: PCT/U52012/069080 0 (IV) ; a diester of the formula V: (V) ; and, optionally, a diester of the formula Vi: (Vl). - R1 and/or R2 can individually comprise a hydrocarbon having from about 1 to about 8 carbon atoms, typically, , ethyl, propyl, isopropyl, butyi, isobutyt, n—butyl, isoamyl, hexyl, , or octyl. ln such embodiments, the blend typically comprises (by weight of the blend) (i) from about 5% to about 30% of the diester of a IV, (ii) from about 70% to about 95% of the diester of formula V, and (iii) from about 0% to about % of the diester of formula Vl. More typically, the blend typically comprises (by —16~ PCT/U82012/069080 weight of the blend): (i) from about 6% to about 12% of the r of formula IV, (ii) from about 86% to about 92% of the diester of formula V, and (iii) from about 0.5% to about 4% of the diester of formula Vi. [0093} Most typically, the blend comprises (by weight of the blend): (i) about 9% of the diester of formula M, (ii) about 89% of the diester of formula V, and (iii) about 1% of the diester of formula Vi. The blend is generally characterized by a flash point of of 98 °C, a vapor pressure at 20 °C of less than about 10 Pa, and a distillation temperature range of about 200—275 °C. in another embodiment, the solvent can include other ts, including but not limited to aliphatic or acyclic hydrocarbons solvents, halogenated solvents, aromatic hydrocarbon solvents, cyclic es, unsaturated hydrocarbon ts, rbon solvents, polyols, alcohols including short chain alcohols, ketones or mixtures thereof.

The e nd utilized as the solvent or in the solvent blend described herein includes those of formula (l), below: CH2‘J—OHn O O R6 7 in which: R5 and R7, which are identical or different, represent hydrogen Of a C1~C14 group or radical. in one embodiment, R5 and R7 are individually selected from an alkyl group, alkenyl group or phenyl radical. in some embodiments, “n” is an integer of 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11 or 12. Typically, "n" is an integer ranging from 1 to 4 or “‘n’ is an integer ranging from 1 to 2. -17.. 2012/069080 in one particular embodiment, R6 and R7 are radicals individually ed from , ethyl, n-propyl, isopropyi or isobutyi radical. in one embodiment the dioxolane compound is of formula (l) is 2,2—dimethyl— 1,3~dioxolane—4—methanol. in another embodiment, the dioxolane compound of formula (1) is 2,2—diisobutyl—i ,3—dioxolane-4—methanol (also known by the acronym IIPG, for the synonym ’l~isobutyl-isopropylidene glycerol). in one embodiment, a nd utilized as the solvent or as a component in the solvent blend is a compound of general formula (ll): RgooC—A—CONR4R5 (II), According to one embodiment, the expression "compound“ denotes any compound corresponding to the general formula (It). In other embodiments, the term‘ "compound" also refers to mixtures of several molecules corresponding to general formuia (II). it may therefore'be a moiecule of formula (ll) or a e of l les of formula (ll), wherein both fall under the definition of the term “compound” when referring to formula (ll).

The R3, R4 and R5 groups can be, in some embodiments. identical or, in other embodiment, ent. In one embodiment, may be groups chosen from C1-Cgo alkyl, aryl, l or arylalkyl groups or the phenyl group. in another embodiment, may be groups chosen from C1612 alkyl, aryl, aikaryl or arylalkyl groups or the phenyl group.

Mention is made especially of Rhodiasolv® PolarClean (Manufactured by Rhodia Inc. of Cranbury, NJ). The R4 and R5 groups may optionally be substituted. In one particuiar embodiment, the groups are substituted with hydroxyl groups PCT/U52012/069080 In one embodiment, R3 group is chosen from methyl, ethyl, propyl, isopropyl, n—butyl, isobutyl, n-pentyl, isopentyl, isoamyi, n-hexyl, cyclohexyl, 2-ethylbutyl, n-octyl, isooctyl, 2—ethylhexyl, tridecyl groups.

R4 and R5 groups, which are identical or different, in one embodiment, may especially be chosen from methyl, ethyl, propyl (n—propyl), isopropyl, n-butyl, isobutyl, n- pentyl, amyl, isoamyl, hexyl, cyclohexyl or hydroxyethyl groups. The R4 and R5 groups may also be such that they form, together with the nitrogen atom, a morpholine. piperazine or dine group. According to some embodiments, R4 and R5 are each methyl, or R4 and R5 are each ethyl, or R4 and R5 are each hydroxyethyl.

According to one embodiment, ifA comprises a linear group offormula -— CH2-- CH2—- andlor of formula —- CH2" CH2-- CH2-— CH2—— and/or of formuta --( CH2)3-— then it is a mixture of A groups. According to one particular embodiment. ifA is linear, then it is a e ofA groups, for example a mixture of two or three —~ CH2» CH2" (ethylene); —- CHz— CH2~ CH2-- pylene); and —— CH2—— CH2—- CH2—— CH2" (n— butylene) groups (or isomers thereof). ing to a first particular ment of the invention, the A group is a divalent linear alkyl group chosen from the groups of the fotlowing formulae: -- CH2—— CH2" (ethylene); —— CH2-- CH2—- CH2" pylene); —- CH2“ CH9;- CH2~- CH2» (n- butylene), and mixtures thereof. ] ing to such embodiment, the compound is a mixture according to the following mixture of molecules: R3000-(CH2)2-CONR4R5; R3000-(CH2)3~CONR4R5; and WO 2013090324 PCT/U82012/069080 RgOOC-(CH2)4-CONR4R5 According to another particular embodiment of the invention, the A group is a divalent branched alkyl group chosen from the groups of the following formulae: CH(CH3)— CH2—-CHz--; --CH(CZH5)—~CH2—-; and, optionally, —- CH2" CHz—~ CH2—— CH2“; as well as mixtures f.

] According to such embodiment, the compound is a mixture according to the following mixture of molecules: R300C-CH(CH3}(CH2)2-CONR4R5; R3000—CH(02H5)CH2-CONR4R5 ; and, optionally, R3000—(CH2)4—CONR4R5 According to one particular variant in this first embodiment, the compound of the invention is chosen from the ing compounds: MeOOC-- CH2» CHg—CONMeg; MeOOC—— CH2" CH2— CH2—-CON Meg; MeOOC—- CH2" (3ng CH2—-CON M82, as a mixture with MeOOCuCng CH2~—C H2» CH2--CON M92 and/or with MeOOC—— CH2-- ON M92.

According to another embodiment of the invention, the A group is a divalent branched alkylene group having one of the following ae (Ila), (lib), (tic), (Illa) and (lllb), or a mixture of at least two groups chosen from the groups of ae (lla), (lib) and (lie) or from the groups of formulae (His) and (Illb), or a mixture of at least two , one chosen from the groups of formulae (Eta), (lib) and (llc) and the others chosen from the groups of formulae (Illa) and (lllb): --(CHR9)y--(CHR3)x—(CHR9)z—-CHp_--CH2--(Ila) PCT/U52012/069080 --CH2--CH2—-(CHRg)z-—(CHR3)x--(CHR9)y-- (llb) -—(CHR9)Z-— CH2—-(CHR8)x—-CH2~—(CHR9)y—— (llc) {001231 -—(CHR9)y——(CHR3)x—(CHR9)z-—CH2—- (Illa) — CH2—-(CHR9)z--(CHR3)x—~(CHRg)y-- (lllb) where: x is an integer greater than 0; y is an average integer greater than or equal to 0; 2 is an average integer greater than or equal to 0; R8, which is identical or different, is a 01—05, preferably C1—C4, alkyl group; and R9, which is identical or different, is a en atom or a 01—05, preferably C1vC4, alkyl group. In this particular embodiment, the A group is preferably a group such that y and z are 0.

In one embodiment, in formula (Ila) and/or in the formula (lib): x is 1; y and z are 0; R3 is methyl.

In another ment, in the formula (Illa) and/or in the a (Illb): x is 1; y and z are 0; R3 is ethyl. ing to another embodiment, the compound of the invention is chosen from the following compounds, and mixtures f: MeOOC—Amg-CONMeg; MeOOC-AES-CONMez; PeOOC—AM9~CON M62; PeOOC~AEs—CONMeg; CycloOOC-Amg—CONMez; CycloOOC-Aes-CONMez; AMg—CONMeg; EhOOC-AEs-CONMez; PeOOC-Amg-CONEtg; PeOOC-AEs—CONEtz; CycloOOC—AMG-CONEtz; CycloOOC—AES—CONEtz; BuOOC~AMG-CONEt2; BuOOC—AEs—CONEtg; BuOOC-AMG-CONMez; BuOOC—AEs—CONMez; EtBuOOC-AMG—CONMez; ] EtBuOOC-AEs-CONMeg; n-HeOOC-AMg-CONMez; n—HeOOC—AEs—CONMeg; where AMG represents an MGa group of formula —-CH(CH3)——CHz--CH2--, or MGb group of formula --CH2-—CH2~—CH(CH3)-- or a mixture of MGa and MG, groups; AES represents an ESa group of a ~—CH(CgH5)--CH2—-, or ES!> group of formula ——CH2—~CH(CZH5)—— or a e of ESa and E313 groups; Pe represents a pentyl group, preferably an isopentyl or isoamyl group; Cyclo represents a cyclohexyl group; [0015?] Eh represents a 2~ethylhexyl group; ] Bu represents a butyl group, preferably an l or tert-butyl group; PCT/U52012/069080 EtBu represents an ethylbutyi group; and n-He represents an n—hexyl group.

It is mentioned that according to one particular embodiment, the compound of the invention is a compound different from the following compounds: MeOOC--CHEt-CH2—-CON M62; MeOOC--CH2——CH(CH3)-—CH2—-CONMe2; MeOOC-~CH2——CH2«~CH2--CONMeg; and MeOOC-—CH2--CHg—-CONMe2; if the latter are not used as a mixture with other compounds corresponding . to a (ll).

It is ned that according to one even more particular variant of one or the other of the particular embodiments of the ion, the compound of the invention is a novel compound of the ion, different from the following compounds mixtures, ifthe , individually, are not used as a mixture with other compounds ponding to formula (it): MeOOC—-CHEt~CH2--CONMe2; —CH2~-CH(CH3)--CH2—-CONMe2; MeOOC--CH2—-CH2—-CH2~-CONMeg; MeOOC—~CH2——CH2--CONMe2; mixture of PhOOC~~CH(CH3)~~CH2—~CONEtz and PhOOC—-CH2--CH2~~CHg-- CONEtz; EtOOC——CH(CH3)-~CHz—CONEtz; MeOOC-—CH(CH3)--CH2—-CONEt2; 2012/069080 Me—CH(OMe)-OOC-—CH(CH3)--CH2——CONEtg; CyclohexyI-OOC--CH(CH3)-~CH2--CONEtz; Ph—CH2000--CH(CH3)--CH2--CONEtg; p—cresyl-OOC--CH(CH3)——CH2—CONEt2; [001 79] mixture of EtOOC—-CHEt-CH2~—CON E12, EtOOC--CH(CH3)-—CH2—«CH2—~ CONEtg and EtOOC~-CH2—-CH2—-CH2--CH2~—CONEtz; and [001 80] -CH2--CH(CH3)~—CH2——CONH(n-butyl).

It is mentioned that according to one even more particular variant of one or the other of the particular embodiments of the ion, the compound of the ion is a novel compound of the invention, different from the ing compounds or mixtures, ifthe latter, individuaily, are not used as a mixture with other compounds corresponding to formula (ll): OOC-—CH2-—CH2--CONEt2 CeH13--OOC--(CHz)8—-CON(03H7)2 Cal—l17——OOC—-(CH2)3--CON(C4H9)2 CgH17~~OOC—~(CH2)3——CON(CaH17)2.

In one embodiment, it is possible to use the foliowing compounds as a mixture with other compounds corresponding to formula (ll): MeOOC—~CHEt—CH2—-CONMez; MeOOC~—CH2»CH(CH3)—CH2—CONMeg; MeOOC—-CH2~CH2~~CH2--CONMe2; {001901 MeOOC--CH2--CH2--CONM82; PCT/U52012/069080 e of PhOOC—-CH(CH3)-~CH2—~CONEt2 and PhOOC—-CH2—-CH2—-CH2-- CONEtZ; EtOOC--CH(CH3)--CH2“CONEt2; [001 93] MeOOC--CH(CH3)--CH2--CON Etz; Me—CH(OMe)—OOC—-CH (CH3)——CH2—CON E12; Cyclohexyl-OOC——CH(CH3)-—CH2—~CONEt2; ' OOC——CH(CH3)-CH2--CONEtg; p—cresyl—OOC——C H(CH3)--CH2--CONEt2; [001 93] mixture of EtOOC——CHEt—CH2—-CONEt2, EtOOC——CH(CH3)--CH2—-CH2—— CONEtg and —CH2--CH2~-CHp_——C H2——CONEt2; MeOOC—-CH2——CH(CH3)--CH2--CONH(n—butyl); C4Hg--OOC--CH2--CH2--CONEt2; ] CGH13——OOC—-(CH2}g--CON(03H7)2; C3H17——OOC--(CH‘2)a——CON(C4Hg)2; and CBH17“"OCC"(CH2)8”CON(CBH17)2- It is mentioned that according to one still more particular variant of one or the other of the particular embodiments of the invention, the ing compounds or mixtures are not used: MeOOC——CHEt—CH2——CONMe2; MeOOC--CH2--CH(CH3)—-CH2——CONM82; MeOOC-—CH2——CH2—-CH2—-CONMeg; MGOOC--CH2--CH2--CONM62; W0 20131090324r PCT/U82012/069080 ] mixture of PhOOC—~CH(CH3)——CH2——CONEt2 and PhOOC—-CH2—-CH2-—CH2—- CONEtz; EtOOC-~CH(CH3)--CH2—-CONEt2; MeOOC~~CH(CH3)——CH2——CONEt2; OMe)—OOC—-CH(CH3)--CH2-CONEt2; Cyclohexyl-OOC-~CH(CH3)——CH2—-CONEt2; Ph—CHZOOC——CH(CH3)-—CH2——CONEt2; p».cresyl—OOC—~CH(CH3)—-CH2——CONEt2; mixture of EtOOCwCHEt-CHg—~CONEt2, EtOOC~CH(CH3)——CH2-—CH2-- CONEtz and EtOOC--CH2--CH2—-CHz--CH2—-CONEtg; and MeOOC—~CH2—-CH(CH3)—-CH2——CONH(n—butyi).

It is mentioned that according to one still more particular variant of one or the other of the particular embodiments of the invention, the following compounds or mixtures are not used: C4Hg~-OOC--CH2--CH2—-CONEt2; C5H13~OOC--(CH2)8--CON(03H7)2; ] CaH17~—OOC—-(CH2)s—-CON(C4H9)2; 03H]7--OOC~-(CH2)3~-CON(CsH17)2.

According to one embodiment, the esteramide has a melting point that is less than or equal to 20 °C, preferably 5 °C. preferably 0°C.

In one particular embodiment, R3 is a group chosen from saturated or unsaturated, linear or branched, optionally cyclic, optionally ic hydrocarbon- based groups sing an e number of carbon atoms ranging from 1 to 36. R4 W0 2013f090324 and R5, which are identical or different, are groups-chosen from saturated or unsaturated, linear or branched, optionally cyclic, optionally aromatic, optionally substituted hydrocarbon—based groups comprising an average number of carbon atoms ranging from 1 to 36. it is possible for mend R5 to form a ring together, and in some embodiment, the ring is ally substituted andlor optionally comprises a heteroatom. in some embodiments, A is a linear or branched divalent alkyi group comprising an average number of carbon atoms ranging from 1 to 20, in some embodiments, from 2 to 12, in other ments, from 2 to 8, in yet other embodiments, from 2 to 4, In one embodiment, the solvent comprises amides, alkyl amides, or dialkyl amides. in an alternative embodiment, one component in the t blend comprises an amide, alkyl amide, and/or dialkyl amide. in one particular embodiment, the solvent or solvent blend is imethylamide (ADMA). The alkyl group is a C1 —050 alkyl group, more typically a C2 4330 aikyl group, even more typically, a C2 -C20 alkyl group.

In one particular embodiment, the alkyldimethylamide is N,N—dimethyldecanamide bility ) or N,N~dimethyloctanamide (miscibility 0.43%), or es therof.

Mention is made especially of the compounds sold by Rhodia, Rhodiasolv® ADMA81O and Rhodiasolv® ADMA10. in another ment, the t system can contain one or more surfactants. The surfactant can be any number of cationic, amphoteric, mitterionic, anionic or nonionic surfactants, tives thereof, as well as blends of such surfactants in one embodiment, the nonionic surfactants generally includes one or more of for example amides such as alkanolamides, ethoxylated alkanoiamides, ethylene PCT/U52012/069080 bisamides; esters such as fatty acid esters, glycerol esters, ethoxylated fatty acid esters, sorbitan , ethoxylated can; ethoxylates such as alkylphenol ethoxylates, l ethoxylates, tristyrylphenol ethoxylates, mercaptan ethoxylates; pped and EOIPO block copolymers such as ethylene oxide/propylene oxide block copolymers, chiorine capped ethoxylates. functional block copolymers; amine oxides such lauramine oxide, cocamine oxide, stearamine oxide, stearamidopropylamine oxide, palmitamidopropylamine oxide, decylamine oxide; fatty aicohols such as decyl alcohol, lauryl l, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyi alcohol and linolenyl alcohol; and alkoxylated alcohols such as ethoxylated lauryl alcohol, trideceth alcohols; and fatty acids such as lauric acid, oleic acid, stearic acid, myristic acid, cetearic acid, isostearic acid, linoleic acid, iinolenic acid, ricinoleic acid, elaidic acid, arichidonic acid, myristoleic acid and es thereof.

In another embodiment, the non-ionic surfactant is a glycol such as polyethylene glycol (PEG), alkyl PEG esters, polypropylene glycol (PPG) and derivatives thereof. In one embodiment, the surfactant is an l ethoxylate, an alkyl phenol ethoxylate or a terpene iate. in one exemplary embodiment, the surfactant is a C5-C13 alcohol ethoxylate and, more typically, a (33-012 alcohol ethoxylate. } in another embodiment, the surfactant is a cationic surfactant. The cationic surfactant includes but is not d to quaternary ammonium compounds, such as cetyl trimethyi ammonium bromide (aiso known as CETAB or cetrimonium bromide), cetyl trimethyl ammonium chloride (also known as cetrlmonium chloride), myristyl PCT/U52012/069080 trimethyl ammonium bromide (also known as myrtrimonium bromide 0r Quatemium-lS), stearyl dimethyl distearyldimonium chloride, l dimonium chloride, stearyl octyldimonium methosulfate, dihydrogenated palmoylethyl hydroxyethylmonium ulfate, isostearyl benzylimidonium chloride, cocoyl benzyl hydroxyethyl olinium chloride, dicetyl dimonium chloride and distearyldimonium chloride; isostearylaminopropalkonium chloride or olealkonium chloride; behentrimonium chloride; as well as mixtures thereof.

In another embodiment, the tant is an anionic surfactant. The anionic surfactant includes but is not limited to linear alkylbenzene sulfonates, alpha olefin sulfonates, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfates, alkyl sulfonates, alkyl alkoxy carboxylates, alkyl alkoxylated sulfates, monoalkyl phosphates, diatkyl phosphates, sarcosinates, uccinates, isethionates, and es, as well as es thereof. Commonly used anionic surfactants that are le as the anionic surfactant ent of the composition of the present invention include, for example, ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, anolamine h sulfate, hanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamlne lauryl sulfate, diethanolamlne laureth sulfate, iauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium-monoalkyl phosphates, sodium dialkyl phosphates, sodium lauroyl inate, lauroyl sarcosine, cocoyl sarcosine, ammonium cocyl sulfate, ammonium lauryl sulfate, sodium cocyl sulfate, sodium trideceth sulfate, sodium tridecyl e, ammonium trideceth sulfate, ammonium PCT/U82012/069080 yl sulfate, sodium cocoyl isethionate, disodium laureth sulfosuccinate, sodium methyl oteoyl taurate, sodium laureth carboxylate, sodium trideceth carboxylate, sodium lauryl sulfate, potassium cocyl sulfate, potassium lauryl sulfate, monoethanolamine cocyl sulfate, sodium trideoyl benzene sulfonate, and sodium dodecyl e sulfonate. Branched c surfactants are particularly red, such as sodium trideceth sulfate, sodium tridecyl sulfate, ammonium trideceth sulfate, ammonium tridecyl sulfate, and sodium trideceth carboxylate. {00231} Any amphoteric tant that is acceptable for use includes but is not limited to derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group. Specific examples of le amphoteric surfactants include the alkali metal, alkaline earth metai, ammonium or substituted um salts of alkyl amphocarboxy glycinates and alkyl amphocarboxypropionates, aikyl amphodipropionates, alkyl amphodiacetates, alkyl amphoglycinates, and alkyl amphopropionates, as well as alkyl iminopropionates, alkyl iminodipropionates, and alkyl amphopropylsulfonates such as for example, cocoamphoacetate cocoamphopropionate, cocoamphodiacetate, lauroamphoacetate, lauroamphodiacetate , lauroamphodipropionate, lauroamphodiacetate, cocoamphopropyl sulfonate caproamphodiacetate, caproamphoacetate, caproamphodipropionate, and stearoamphoacetate.

Suitable zwitterionic surfactants include alkyl es, such as cocodimethyl ymethyl e, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha- -30_ W0 201311190324 PCT/U82012/069080 carboxy-ethyl e, cetyl dimethyl carboxymethyl betaine, lauryl bis-(Z—hydroxy— ethyl)oarboxy methyl betaine, l bis—(2-hydroxy-propyl)carboxymethyl betalne, oleyl dimethyl gamma-carboxypropyl e, and lauryl bis-(2-hydroxypropyl)alpha- carboxyethyl betaine, amidopropyl betaines, and alkyl sultaines, such as cocodimethyl ropyt betaine, stearyldimethyl sulfopropyl betaine, lauryl dlmethyl sulfoethyl betaine, lauryl bis—(2»hydroxy—ethyl)sulfopropyl betaine, and alkylamidopropylhydroxy sultaines.

E00233] The solvent system described herein are characterized by having improved stability of NBPT; improved solubility characteristics; low toxicity of the solvents; good storage characteristics; and good adsorption characteristics onto the urea—containing fertilizers and excellent miscibility with liquid urea containing fertilizer formulations. {00234} Exgeriments The solvent systems embodied herein were screened to assess compatibility with NBPT. To e each sample, the components (NBPT, solvents, and dye) were combined and d at room temperature until uniform. The samples were then vacuum—filtered through Whatman 1 filtration paper to remove any undissotved pigment.

A combination of solvents was used to meet the concentration requirements and stabitity characteristics. The solvents tested that ed in some degree of s with select molecular structures are as follows: Table 1 RDQSS-‘l 65—01 NBPT 210% Rhodiasolv Polarclean 30.5% Purasolv EL 48.2% Dye 0.3% 100. % PCT/U82012/069080 From Table 1, Polarclean is Methyl-S-(dimethylamino)methyl oxopentanoate and Purasolv EL is an Ethyl—(S)-3actate.

] Table 2 ROSES-16502 NBPT 21.0% Rhodiasolv ADMA 30.9% Purasolv EL 43.5% Water 3.2% Urea 1.1% Dye 0.3% 100.00% Table 3 R0985—165-08 NBPT 21.00% Rhodiasolv ADMA 27.50% Purasolv EL 51.20% Dye 0.3% 100.00% Table 4 R0985-167—01 NBPT 21.00% Augeo SL491 59.16% Rhodiasolv Ll-TEC 19.54% Dye 0.3% 100.00% From Table 4, Rhodiasolv Ll«TEC is a proprietary blend of c esters comprising a dialkyl methylglutarate as the primary dibasic ester, along with one or more additional c esters.

Table 5 I R0985—167—02 I -32..

PCT/U82012/069080 NBPT 26.65% 32.50 Augeo SL491 54.65% 69.15 Rhodiasolv Li-TEC 18.4% 22.98 Dye 0.3% 0.38 100.00% From the Tables above, aii blend components are suitable for use in fertilizer applications in the United States. The formulations, and specially Table 5, meets stability and requirements and ation requirements, as compatible with urea prills, UAN, and passes the smell test.

The present invention, therefore, is well adapted to carry out the objects and attain the ends and advantages mentioned. as well as others inherent therein. While the invention has been depicted and described and is defined by nce to ular preferred embodiments of the ion. such references do not imply a limitation on the invention, and no such limitation in scope is to be inferred.

Claims (22)

CLAIMS What is claimed is:

1. A ition comprising: a) at least one alkyl thiophosphoric triamide; and b) a solvent comprising at least one dioxolane compound of formula (Ia): CH4—OHn Re (la), wherein R5 and R7 individually comprises an alkyl group, an alkenyl group, or a phenyl group, wherein n is an integer of from 1 to 10.

2. The composition of claim 1 further comprising a solvent ed from the group consisting of: A) at least one dibasic ester; B) at least one compound of formula (lla): R3000-A-CONR4R5 (”3), wherein R3 ses a 01-036 alkyl group; wherein R4 and R5 individually comprise a 01-035 alkyl group, wherein R4 and R5 can optionally together form a ring; and wherein A is a linear or branched nt Cz-Ce alkyl group; c) at least one alkyldimethylamide; d) at least one alkyl lactate; e) ethyl levulinate; f) at least one alkyoxyalcohol, ether alcohol, amine alcohol, amino alcohol or alcohol; g) at least one ine or glycerine derivative; h) at least one alkylene carbonate; and i) any combination f.

3. The composition of claim 1 wherein the alkyl thiophosphoric triamide is N-(n-butyl)- thiophosphoric triamide.

4. The composition of claim 1 wherein the alkyl thiophosphoric triamide is present in an amount between about 0.5 % by weight of the composition and about 50 % by weight of the composition.

5. The composition of claim 1 wherein the alkyl thiophosphoric triamide is present in an amount between about 1 % by weight of the composition and about 30 % by weight of the composition.

6. The ition of claim 2 n R3 is selected from the group consisting of a saturated 01-035 alkyl group, an unsaturated C1-Cae alkyl group, a linear C1-C36 alkyl group, a ed 01-035 alkyl group, a cyclic C1—C35 alkyl group, and an aromatic C1- 036 alkyl group.

7. The composition of claim 2 wherein R4 and R5 individually comprise a ted C1- C35 alkyl group, an unsaturated 01—036 alkyl group, a linear C1-C36 alkyl group, a branched 01-035 alkyl group, a cyclic C1-C3e alkyl group, or an aromatic 01-036 alkyl group.

8. The composition of claim 2 wherein the at least one dibasic ester comprises at least two of: dialkyl methylglutarate, dialkyl ethylsuccinate, dialkyl adipate, dialkyl ate or dialkyl glutarate.

9. The composition of claim 2 wherein the at least one dibasic ester comprises a blend of dialkyl methylglutarate, dialkyl ethylsuccinate and, optionally, dialkyl adipate.

10. The composition of claim 2 wherein the at least one c ester comprises a blend of dialkyl adipate, dialkyl succinate and dialkyl glutarate.

11. The composition of claim 2 wherein the alkyl lactate is a C1—C8 alkyl lactate.

12. The composition of claim 2 wherein the alkoxyalcohol is 2—butoxyethanol.

13. The ition of claim 2 wherein the at least one alkylene carbonate is propylene carbonate.

14. The composition of claim 1 wherein the composition is a flowable liquid composition. ~36—

15. The composition of claim 14 n the flowable liquid composition is a homogenous solution.

16. The ition of claim 14 wherein the flowable liquid composition is a mixture.

17. The composition of claim 2 wherein the amine alcohol is ed from the group consisting of ethanolamine, olamine, dialkyl alkanolamines, methanolamine, and any combination thereof.

18. A method for preparing an ltural composition comprising contacting the composition of claim 1 with a nitrogen-based fertilizer composition.

19. The method of claim 18 wherein the nitrogen-based fertilizer composition is in granular form.

20. The method of claim 18 wherein the nitrogen-based fertilizer composition is in substantially liquid form.

21. The composition of any one of claims 1 to 17, substantially as herein described with reference to any one of the Examples thereof.

22. The method of any one of claims 18 to 20, substantially as herein described with reference to any one of the Examples thereof.