(19)
(11)EP 3 365 348 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
17.06.2020 Bulletin 2020/25

(21)Application number: 16788881.7

(22)Date of filing:  17.10.2016
(51)International Patent Classification (IPC): 
C07F 9/22(2006.01)
C05C 3/00(2006.01)
C05F 3/00(2006.01)
C05C 1/00(2006.01)
C05C 9/00(2006.01)
(86)International application number:
PCT/US2016/057352
(87)International publication number:
WO 2017/070048 (27.04.2017 Gazette  2017/17)

(54)

FERTILIZER STABILIZER COMPOSITION COMPRISING A LOW VOC AND LOW ODOR AROMATIC OIL

DÜNGERSTABILISATORZUSAMMENSETZUNG ENTHALTEND EIN AROMATISCHES ÖL MIT NIEDRIGEM ANTEIL AN FLÜCHTIGEN ORGANISCHEN VERBINDUNGEN UND GERINGEM GERUCH

COMPOSITION STABILISATRICE D'ENGRAIS COMPRENANT UNE HUILE AROMATIQUE À FAIBLE TENEUR EN COMPOSÉS ORGANIQUES VOLATILS (COV) ET FAIBLE ODEUR


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 19.10.2015 US 201562243426 P

(43)Date of publication of application:
29.08.2018 Bulletin 2018/35

(73)Proprietor: Dow Global Technologies LLC
Midland, MI 48674 (US)

(72)Inventor:
  • NG, Sze-Sze
    Midland, MI 48674 (US)

(74)Representative: Boult Wade Tennant LLP 
Salisbury Square House 8 Salisbury Square
London EC4Y 8AP
London EC4Y 8AP (GB)


(56)References cited: : 
WO-A1-2014/028767
WO-A1-2016/170784
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    BACKGROUND OF THE INVENTION



    [0001] Nitrogen fertilizer is an important input in farming as it is correlated to yield. After nitrogen fertilizer is applied to the ground it can be lost through volatilization or leaching to ground water as the fertilizer undergoes the nitrogen cycle. To minimize loss of investment and environmental impact, nitrogen fertilizer is often treated with fertilizer stabilizer. Common fertilizer stabilizer products are for example AGROTAIN, N-SERVE, and NUTRISPHERE-N.

    [0002] N-Alkyl thiophosphoric triamide urease inhibitor, e.g., N-butyl thiophosphoric triamide (NBPT), is used in agriculture to stabilize nitrogen fertilizer urea. It is most commonly formulated in a mixture of N-methyl-2-pyrrolidone (NMP) and propylene glycol (as in AGROTAIN™ by Koch). NMP is used as a crystal inhibitor but it has high toxicity. Other solvents are also known to be good solvents for NBPT, such as dimethyl sulfoxide (DMSO) (see US Published Patent Application 2015/0143860A1), benzyl alcohol (LIMUS™ by BASF), amino alcohol, and the like.

    [0003] Some glycol ether solvents are known to be good solvents for NBPT (e.g., StabilureN™ by Agra, and see EP 2 032 589 B1). However, not all glycol ethers have the same properties. The alkyl glycol ether solvents are known to dissolve NBPT, but they have a strong odor, a low flash point, and a high volatile organic compound (VOC) content. Another type of alkyl glycol ether known as an effective NBPT carrier is a surfactant in nature, and it causes severe foaming issues in fertilizer solutions which require an antifoaming agent in the formulation (see USP 9,090,516 and USP 9, 096,476). Based on these cited patents, glycol ether surfactant is functionally different from glycol ether solvents even though both are generically called glycol ethers. Glycol ether solvents provide varying degrees of chemical stability to NBPT depending on the specific structure. For example, a solution containing NBPT and dipropylene glycol methyl ether develops a strong yellow color within a month at ambient temperature.

    [0004] An alternative solvent system for NBPT is desired, one that provides an improved user handling experience by reducing solvent odor and eliminating hazardous NMP, and reduces emission of air pollutants by lowering volatile organic content to a minimum level.

    SUMMARY OF THE INVENTION



    [0005] In one embodiment, the invention is a fertilizer stabilizer composition comprising:
    1. (A) two or more glycol ethers of Formula 1

      wherein

      Each of R1 and R3 are independently hydrogen or phenyl with the proviso that R1 and R3 are not simultaneously hydrogen,
      n is an integer of 3-10, and

      R2 is 90 to 100% hydrogen and 0 to 10% of one or more of methyl, ethyl or phenyl; and

    2. (B) at least one fertilizer stabilizer comprising a N-C1-6 thiophosphoric triamide;
    the fertilizer stabilizer composition characterized as having at least one of the following properties:
    1. (1) a vapor pressure of less than or equal to (≤) 1000 Pa (0.01 millimeters of mercury (mmHg)) at 20°C as measured by ASTM E1719,
    2. (2) a flash point equal to or greater than (≥) 93°C (200°F) as measured by ASTM D3278,
    3. (3) a viscosity less than or equal to (≤) 200 centipoise (cP) at 25 °C as measured by ASTM D445,
    4. (4) a hydroxyl number from 100 to 1,000 as measured by ASTM D4274, and
    5. (5) a VOC content less of than or equal to (≤) 50 weight percent (wt%) as measured by ASTM D6886.


    [0006] In one embodiment the invention is a fertilizer composition comprising:
    1. (A) the fertilizer stabilizer composition as described in the preceding paragraph, and
    2. (B) a nitrogen-based fertilizer.


    [0007] In one embodiment, the inventive fertilizer stabilizer composition comprises at least one of a N-C1-6 alkyl thiophosphoric triamide. In one embodiment, the inventive fertilizer stabilizer composition is free, or substantially free, of NMP.

    [0008] The inventive fertilizer stabilizer compositions of this invention have a low flash point and odor profile, a low pour point for easy handling, a low VOC content, and they do not foam in fertilizer solutions, and they provide chemical and thermal stability to NBPT.

    DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT


    Definitions



    [0009] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight and all test methods are current as of the filing date of this disclosure.

    [0010] All percentages, preferred amounts or measurements, ranges and endpoints are inclusive, that is, "up to 10" includes 10. "At least" is equivalent to "greater than or equal to," and "at most" is, thus, equivalent "to less than or equal to." Numbers are approximate unless otherwise specifically noted. All ranges from a parameter described as "at least," "greater than," "greater than or equal to" or similarly, to a parameter described as "at most," "up to," "less than," "less than or equal to" or similarly are preferred ranges regardless of the relative degree of preference indicated for each parameter. Thus a range that has an advantageous lower limit combined with a most preferred upper limit is preferred for the practice of this disclosure. The term "advantageous" is used to denote a degree of preference more than required, but less than is denoted by the term "preferably." Numerical ranges are provided within this disclosure for, among other things, the amount of components in the various compositions of the invention.

    Glycol Ethers



    [0011] The fertilizer stabilizer compositions of this invention comprise two or more glycol ethers of Formula 1

    wherein

    Each of R1 and R3 are independently hydrogen or phenyl with the proviso that R1 and R3 are not simultaneously hydrogen,

    n is an integer of 3-10, and

    R2 is 90 to 100% hydrogen and 0 to 10% of one or more of methyl, ethyl or phenyl.

    In one embodiment, if R1 is hydrogen, then R3 is phenyl. In one embodiment, if R1 is phenyl, then R3 is hydrogen. In one embodiment, both R1 and R3 are phenyl. In one embodiment, n is an integer of 3, or 4, or 5, or 6, or 7, or 8, or 9. In one embodiment, n is an integer of 3 to 4, or 5, or 6, or 7, or 8, or 9, or 10; or of 4 to 5, or 6, or 7, or 8, or 9 or 10; or of 5 to 6, or 7, or 8, or 9, or 10; or of 6 to 7, or 8, or 9, or 10; or of 7 to 8, or 9, or 10; or of 8 to 9 or 10; or of 9 or 10. In one embodiment, R2 is at least 91%, or 92%, or 93%, or 94%, or 95%, or 96%, or 97%, or 98%, or 99% to 100% hydrogen. In one embodiment, R2 is at least 1%, or 2%, or 3%, or 4%, or 5%, or 6%, or 7%, or 8%, or 9% to 10% one or more of methyl, ethyl or phenyl. "At least 91%, or 92%, or ..." means that the value of R2 can be a whole number, e.g., 91, 92, etc., or a fractional number, e.g., 91.1, or 92.1, etc. "At least 1%, or 2%, or..." means that the value of R2 can be a whole number, e.g., 1, 2, etc., or a fractional number, e.g., 1.1, or 2.1, etc.

    [0012] "Two or more glycol ethers of Formula 1" means that the liquid composition comprises at least two distinct glycol ethers of Formula 1, e.g., a first glycol ether in which R1 is hydrogen and a second glycol ether in which R1 is phenyl and all other substituents or components of the two glycol ethers are the same; or a first glycol ether in which n is 3 and a second glycol ether in which n is 10 and all other substituents or components of the two glycol ethers are the same; etc. The glycol ethers can differ from one another in more than one substituent or component, and the fertilizer stabilizer composition can comprise any number of different glycol ethers of Formula 1.

    [0013] Based on the total amount of glycol ethers in the fertilizer stabilizer composition, the amount of any on glycol ether can vary widely. Typically, no one glycol ether comprises more than 99 wt% of the total amount of glycol ethers in the fertilizer stabilizer composition, more typically no more than 90, or 80, or 70, or 60, or 50 wt% of the total amount of glycol ethers in the fertilizer stabilizer composition. In one embodiment, glycols other than those of Formula 1, e.g., ethylene and/or propylene glycol, glycerol, polyalkylene glycol, etc., may also be present, and these can be present in either a majority or minority amount of the total glycol content of the fertilizer stabilizer composition, but typically these are present in a minority amount, i.e., they constitute less than 50 wt%, more typically less than 25 wt%, of the total glycol content of the fertilizer stabilizer composition.

    [0014] The glycol ethers of Formula 1 are known compounds and are commercially available, such as DOWANOL™ EPh6.

    Fertilizer Stabilizers



    [0015] The fertilizer stabilizer compositions of this invention comprise one or more fertilizer stabilizers. These stabilizers are N-C1-6 alkyl thiophosphoric triamides. Regarding N-C1-6 alkyl thiophosphoric triamide, the alkyl can be linear or branched, and preferably the alkyl is propyl or butyl. In one embodiment, the fertilizer stabilizer compositions comprise just one fertilizer stabilizer, and in one embodiment that fertilizer stabilizer is a N-C1-6 alkyl thiophosphoric triamide, preferably N-(n-butyl) thiophosphoric triamide (NBPT) or N-(n-propyl) thiophosphoric triamide (NPPT).

    Fertilizer Stabilizer Compositions



    [0016] In one embodiment, the fertilizer stabilizer compositions of this invention comprise 0.01 to 60 wt%, preferably 0.01 to 35 wt% and more preferably 0.01 to 25 wt%, fertilizer stabilizer and 40-99.99 wt%, preferably 65 to 99.99 wt% and more preferably 75 to 99.99 wt% glycol ether.

    [0017] The fertilizer stabilizer compositions of this invention are liquid at ambient conditions (20-25°C and atmospheric pressure), and are typically a solution, i.e., without any significant particulate content. In other words, the fertilizer stabilizer is typically soluble in the glycol mixture, i.e., the two or more glycol ethers of Formula 1 and any additional glycols/solvents that may be present.

    [0018] In one embodiment, the fertilizer stabilizer compositions of this invention have a low volatile organic compound (VOC) content, typically less of than or equal to (≤) 50 weight percent (wt%), more typically ≤ 30 wt%, or ≤ 10 wt%, or ≤ 4 wt%, as measured by ASTM D6886.

    [0019] In one embodiment, the fertilizer stabilizer compositions of this invention have a low vapor pressure, typically less than or equal to (≤) 1000 Pa (0.01 millimeters of mercury (mmHg)), or ≤ 100 Pa (0.001mmHg), or ≤ 10 Pa (0.0001 mmHg), at 20°C as measured by ASTM E1719.

    [0020] In one embodiment, the fertilizer stabilizer compositions of this invention have a viscosity less than or equal to (≤) 200, or ≤ 100, centipoise (cP) at 25 °C as measured by ASTM D445.

    [0021] In one embodiment, the fertilizer stabilizer compositions of this invention have a flash point equal to or greater than (≥) 93°C (200°F), or ≥ 121°C (250°F), as measured by ASTM D3278.

    [0022] In one embodiment, the fertilizer stabilizer compositions of this invention have a hydroxyl number from 100 to 1,000, or from 100 to 800, or from 100 to 600, as measured by ASTM D4274.

    [0023] In one embodiment, the fertilizer stabilizer compositions of this invention have at least two, or at least three, or at least four, or all five of the properties of VOC content, vapor pressure, viscosity, flash point and hydroxyl number as described in the previous embodiments.

    [0024] In one embodiment, the fertilizer stabilizer compositions of this invention consist essentially of 0.01 to 60 wt%, preferably 0.01 to 35 wt% and more preferably 0.01 to 25 wt%, of fertilizer stabilizer and 40-99.99 wt%, preferably 65 to 99.99 wt% and more preferably 75 to 99.99 wt%, two or more glycol ether of Formula 1.

    [0025] In one embodiment, the fertilizer stabilizer compositions of this invention consist essentially of 0.01 to 60 wt%, preferably 0.01 to 35 wt% and more preferably 0.01 to 25 wt%, of at least one of N-C1-6 alkyl thiophosphoric triamide, and 40-99.99 wt%, preferably 65 to 99.99 wt% and more preferably 75 to 99.99 wt%, of two or more glycol ethers of Formula 1.

    [0026] In one embodiment, the fertilizer stabilizer compositions of this invention consist essentially of 0.01 to 60 wt%, preferably 0.01 to 35 wt% and more preferably 0.01 to 25 wt%, of at least one of N-(n-butyl) thiophosphoric triamide (NBPT) or N-(n-propyl) thiophosphoric triamide (NPPT), and 40-99.99 wt%, preferably 65 to 99.99 wt% and more preferably 75 to 99.99 wt% of two or more glycol ethers of Formula 1.

    [0027] In one embodiment, the fertilizer stabilizer compositions of this invention consist of 0.01 to 60 wt%, preferably 0.01 to 35 wt% and more preferably 0.01 to 25 wt%, of fertilizer stabilizer and 40-99.99 wt%, preferably 65 to 99.99 wt% and more preferably 75 to 99.99 wt%, of two or more of glycol ethers of Formula 1.

    [0028] In one embodiment, the fertilizer stabilizer compositions of this invention consist of 0.01 to 60 wt%, preferably 0.01 to 35 wt% and more preferably 0.01 to 25 wt%, of at least one of N-C1-6 alkyl thiophosphoric triamide, and 40-99.99 wt%, preferably 65 to 99.99 wt% and more preferably 75 to 99.99 wt%, of two or more glycol ethers of Formula 1.

    [0029] In one embodiment, the fertilizer stabilizer compositions of this invention consist of 0.01 to 40 wt%, preferably 0.01 to 25 wt%, at least one of N-(n-butyl) thiophosphoric triamide (NBPT) or N-(n-propyl) thiophosphoric triamide (NPPT), and 40-99.99 wt%, preferably 65 to 99.99 wt% and more preferably 75 to 99.99 wt%, of two or more glycol ethers of Formula 1.

    [0030] In one embodiment, the fertilizer stabilizer composition is free, or substantially free, of N-methyl-2-pyrrolidone (NMP). "Free, or substantially free, of" means that the fertilizer stabilizer composition contains less than 1, or less than 0.5, or less than 0.1, or less than 0.05, or less than 0.01, wt% of NMP, based on the weight of the fertilizer stabilizer composition.

    Fertilizer Composition



    [0031] In one embodiment the invention is a fertilizer composition comprising:
    1. (A) the fertilizer stabilizer composition as described above, and
    2. (B) a nitrogen-based fertilizer.
    Any nitrogen-based fertilizer can be used in the practice of this embodiment of the invention, and representative nitrogen-based fertilizers include, but are not limited to, urea, urea ammonium nitrate, ammonia, manure and the like. The fertilizer stabilizer composition can be applied to the nitrogen-based fertilizer in any convenient manner, e.g., spraying the fertilizer stabilizer composition onto solid fertilizer granules and then applying the granules onto or into a soil surface, or mix the fertilizer stabilizer composition directly with one or more liquid fertilizers before spraying the mixture onto a field, or injecting into the fertilizer stabilizer composition into the soil with ammonia, etc. The amount of fertilizer stabilizer composition that is applied to the nitrogen-based fertilizer can vary to convenience, but typically between 0.01 and 10, more typically between 0.01 and 1, and even more typically between 0.01 and 0.5, wt% of the fertilizer stabilizer composition is applied to the nitrogen-based fertilizer, based on the weight of the nitrogen-based fertilizer.

    EXAMPLES


    Example 1 - NBPT Solubility and Storage Study


    Recipe: 20 wt% NBPT / 80 wt% solvent



    [0032] NBPT and solvent are added to a glass vial. The mixture is shaken on an orbital shaker at room temperature (20-25°C). The sample is inspected to determine if all NBPT dissolved at room temperature.

    [0033] Each NBPT mixture is stored at three temperatures, room temperature (20-25°C), 55°C, and -20°C for 4 weeks to evaluate storage stability at elevated, ambient, and sub-ambient conditions. After 4 weeks of storage, the samples are visually inspected for (1) color, which is an indication of degradation, and (2) crystal formation, which is an indicator of insufficient solvency to carry 20 wt% NBPT.

    [0034] NBPT is considered compatible with a solvent if the mixture remained clear, crystal free, and flowable at -20°C for four weeks, and has little color (colorless or pale yellow) after four weeks at 55°C.

    [0035] Only two glycol ethers are identified as compatible with NBPT: methyl CARBITOL™ (as described in WO 2014/028767 A1 and WO 2008/000196 A1, an alkyl glycol ether not of Formula 1, and a comparative sample) and DOWANOL™ EPh6 (a mixture of glycol ethers comprising at least two structures of Formula 1, and an inventive sample). The flash point and vapor pressure of the solvents which produced compatible NBPT mixtures are listed in Table 1 which reports that methyl CARBITOLTM has a low flash point of 91.7°C (197°F) and high vapor pressure of > 10000 Pa (0.1 mmHg) at 20°C, and that DOWANOL™ EPh6 has a high flash point of > 149°C (300°F) and a low vapor pressure of < 10 Pa (0.0001 mmHg) at 20°C.

    [0036] Also note that DOWANOLTM PPH, DOWANOLTM EPH, DOWANOLTM DiPPH, DOWANOLTM DiEPH, and DOWANOLTM DPH 225 - all aromatic glycol ethers which according to Formula 1 have n = 1 (PPh and Eph), n = 2 (DiEPh and DiPPh), or n = 1 and 2 (DPH 255), are not able to produce a NBPT mixture that provides sufficient solvency to carry 20wt% NBPT, as the NBPT mixture with these solvents does not produce a solution that is free of crystal or is flowable at -20°C. This indicates that DOWANOLTM EPh6 is a unique aromatic glycol ether mixture for use as a NBPT solvent.
    Table 1
    NBPT Solubility Test Results
    #TypeSolventRT-20°C 4wks55°C 4 wks ColorSolvent flash point (°C)((°F))Vapor pressure Pa (mmHg) at 20°C
    1   DOWANOL PM X      
    2   DOWANOL DPM X      
    3   DOWANOL TPM X      
    4   DOWANOL PMA hazy X      
    5   DOWANOL DPMA hazy X      
    6   DOWANOL PnP X      
    7 P-Series glycol ethers DOWANOL DPnP X      
    8 DOWANOL PnB hazy X      
    9   DOWANOL DPnB X X      
    10   DOWANOL TPnB X X      
    11   DOWANOL PPh X      
    12   DOWANOL DiPPh X X      
    13   DOWANOL PGDA X X      
    14   PROGLYDE DMM X      
    15   Methyl CARBITOL pale yellow 92(197) 23000 (0.23)
    16   Methoxytriglycol orange    
    17   CARBITOL red    
    18   Ethoxytri glycol red    
    19   Propyl CELLOSOLVE X      
    20   Butyl CELLOSOLVE X      
    21 E-Series glycol ethers Butyl CARBITOL X      
    22 Butoxytriglycol red    
    23 Butyl CELLOSOLVE Acetate X X      
    24   Butyl CARBITOL Acetate X      
    25   Hexyl CELLOSOLVE X      
    26   Hexyl CARBITOL X      
    27   DOWANOL EPh X      
    28   DOWANOL DiEPh X      
    29   DOWANOL EPh6 pale yellow >149 (>300) 10(<0.0001)
    30   DOWANOL DPH 255 X      
    ○= flowable and crystal free
    X= either frozen or contains crystals

    Example 2 - Foam Level of Nitrogen Fertilizer Solutions Containing NBPT Mixtures


    Recipe: 20 wt% NBPT/80 wt% Carrier



    [0037] WO 2014/028715 A1, and USP 9,090,516, teach solvent-free NBPT composition that use a surfactant as the carrier. The problem with using surfactant as a NBPT carrier is foam generation. As is well-known in the fertilizer industry, an observable amount of foam can be generated in an aqueous solution of a surfactant. Solvent does not generate foam because it is not a surfactant. This example demonstrates that DOWANOL™ EPh6 does not generate foam.

    [0038] NBPT mixtures (#31-36) are prepared by mixing NBPT and carrier in a glass vial on an orbital shaker at room temperature (20-25°C). As reported in Table 2, mixtures #31-35 are clear and colorless while #36 is orange in color, an indication of degradation.
    Table 2
    NBPT and Carrier Mixtures
    Component313233343536
    NBPT (g) 20% 20% 20% 20% 20% 20%
    DOWANOL EPh6 (g) 80%          
    BIOSOFT N25-3 (g)   80%        
    TERGITOL 15-S-5 (g)     80%      
    TERGITOL 15-S-9 (g)       80%    
    TERGITOL NP-9 (g)         80%  
    TAE 20EO (g)           80%
     
    Color clear, colorless clear, colorless clear, colorless clear, colorless clear, colorless clear, orange


    [0039] Sixty microliters of NBPT mixtures (#31-36) is added to 30 milliliters (mL) of 342 parts per million (ppm) World Health Organization (WHO) standard hard water. The mixtures are shaken together on the same sample rack for 15 seconds to generate foam. The amount of foam generated immediately (time = 0) is measured with a ruler. The height of the foam is recorded at time = 0, time = 15 minutes, and time = 60 minutes. The higher the foam height, the more foam generated.

    [0040] Similarly, sixty microliters of NBPT mixtures (#31-36) is added to 30 mL of 28-0-0 nitrogen-phosphorus-potassium fertilizer. The mixtures are shaken together on the same sample rack for 15 seconds to generate foam. The amount of foam generated immediately (time = 0) is measured with a ruler. The height of the foam is recorded at time = 0, time = 15 minutes, and time = 60 minutes. The higher the foam height, the more foam generated.

    [0041] As summarized in Table 3 below, NBPT mixture #31 (prepared using DOWANOL™ EPh6 as solvent) does not generate any significant amount of foam (< 2 mm foam) in hard water and in 28-0-0 nitrogen fertilizer. On the other hand, all other examples (#32-#36) with surfactants as NBPT carrier generate a large amount of foam in hard water and in nitrogen fertilizer. Hence, DOWANOL™ EPh6 is not a surfactant as it is not the type of carrier described in WO 2014/028715 A1, and USP 9,090,516.
    Table 3
    Foaming Test Results of NBPT and a Nitrogen-Based Fertilizer
    Time after shaking (min)NBPT MixtureFoam height (mm) of NBPT mixture in 342 ppm hard waterFoam height (mm) of NBPT mixture in 28-0-0 fertilizer
    0 31 1 0
    32 10 5
    33 12 5
    34 50 37
    35 50 35
    36 40 25
    15 31 0 0
    32 7 4
    33 8 3
    34 50 24
    35 50 25
    36 20 20
    60 31 0 0
    32 6 4
    33 5 2
    34 30 9
    35 30 25
    36 9 11



    Claims

    1. A fertilizer stabilizer composition comprising:

    (A) two or more glycol ethers of Formula 1

    wherein

    each of R1 and R3 are independently hydrogen or phenyl with the proviso that R1 and

    R3 are not simultaneously hydrogen,

    n is an integer of 3-10, and

    R2 is 90 to 100% hydrogen or 0 to 10% of one or more of methyl, ethyl or phenyl; and

    (B) at least one fertilizer stabilizer comprising a N-C1-6 alkyl thiophosphoric triamide; the fertilizer stabilizer composition characterized as having at least one of the following properties:

    (1) a vapor pressure of less than or equal to (≤) 1,000 Pascal (Pa) at 20°C as measured by ASTM E1719,

    (2) a flash point equal to or greater than (≥) 200°F (93°C) as measured by ASTM D3278,

    (3) a viscosity less than or equal to (≤) 200 centipoise (cP) at 25 °C as measured by ASTM D445,

    (4) a hydroxyl number from 100 to 1,000 as measured by ASTM D4274, and

    (5) a VOC content less than or equal to (≤) 50 weight percent (wt%) as measured by ASTM D6886.


     
    2. The fertilizer stabilizer composition of Claim 1 in which the at least one fertilizer stabilizer is N-butyl thiophosphoric triamide (NBPT).
     
    3. The fertilizer stabilizer composition of Claim 1 comprising 40-99.99 wt% of the two or more glycol ethers of Formula 1, and 0.01-60 wt% of the fertilizer stabilizer.
     
    4. The fertilizer stabilizer composition of Claim 1 in which R1 of Formula 1 is hydrogen and R3 of Formula 1 is phenyl.
     
    5. The fertilizer stabilizer composition of Claim 1 in which R1 of Formula 1 is phenyl and R3 of Formula 1 is hydrogen.
     
    6. The fertilizer stabilizer composition of Claim 1 in which the fertilizer stabilizer is N-C1-6 alkyl thiophosphoric triamide, and the alkyl is propyl or butyl.
     
    7. The fertilizer stabilizer composition of Claim 1 further comprising glycols other than the glycol ethers of Formula 1.
     
    8. The fertilizer stabilizer composition of Claim 1 having at least two of the properties of vapor pressure, flash point, viscosity, hydroxyl number and VOC content.
     
    9. The fertilizer stabilizer composition of Claim 1 having at least three of the properties of vapor pressure, flash point, viscosity, hydroxyl number and VOC content.
     
    10. The fertilizer stabilizer composition of Claim 1 having at least four of the properties of vapor pressure, flash point, viscosity, hydroxyl number and VOC content.
     
    11. The fertilizer stabilizer composition of Claim 1 having all five of the properties of vapor pressure, flash point, viscosity, hydroxyl number and VOC content.
     
    12. A fertilizer composition comprising:

    (A) the fertilizer stabilizer composition of Claim 1, and

    (B) a nitrogen-based fertilizer.


     
    13. The fertilizer composition of Claim 12 in which the nitrogen-based fertilizer is at least one of urea, urea ammonium nitrate, ammonia and manure.
     
    14. The fertilizer composition of Claim 12 in which the fertilizer stabilizer composition comprises between 0.01 and 10 wt% of the fertilizer composition based on the weight of the nitrogen-based fertilizer.
     


    Ansprüche

    1. Eine Düngerstabilisatorzusammensetzung, die Folgendes beinhaltet:

    (A) zwei oder mehr Glykolether der Formel 1

    wobei

    R1 und R3 jeweils unabhängig Wasserstoff oder Phenyl sind, mit der Maßgabe, dass R1 und R3 nicht gleichzeitig Wasserstoff sind,

    n eine ganze Zahl von 3-10 ist, und

    R2 90 bis 100 % Wasserstoff oder 0 bis 10 % von einem oder mehreren von Methyl, Ethyl oder Phenyl ist; und

    (B) mindestens einen Düngerstabilisator, der ein N-C1-6-Alkyl-Thiophosphortriamid beinhaltet;

    wobei die Düngerstabilisatorzusammensetzung durch mindestens eine der folgenden Eigenschaften aufweisend gekennzeichnet ist:

    (1) einen Dampfdruck von weniger als oder gleich (≤) 1 000 Pascal (Pa) bei 20 °C, wie gemessen durch ASTM E1719,

    (2) einen Flammpunkt, der gleich oder größer als (≥) 200 °F (93 °C), wie gemessen durch ASTM D3278, ist,

    (3) eine Viskosität von weniger als oder gleich (≤) 200 Centipoise (cP) bei 25 °C, wie gemessen durch ASTM D445,

    (4) eine Hydroxylzahl von 100 bis 1 000, wie gemessen durch ASTM D4274, und

    (5) einen VOC-Gehalt von weniger als oder gleich (≤) 50 Gewichtsprozent (Gew.-%), wie gemessen durch ASTM D6886.


     
    2. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, wobei der mindestens eine Düngerstabilisator N-Butylthiophosphortriamid (NBPT) ist.
     
    3. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, die 40-99,99 Gew.-% der zwei oder mehr Glykolether der Formel 1 und 0,01-60 Gew.-% des Düngerstabilisators beinhaltet.
     
    4. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, wobei R1 der Formel 1 Wasserstoff ist und R3 der Formel 1 Phenyl ist.
     
    5. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, wobei R1 der Formel 1 Phenyl ist und R3 der Formel 1 Wasserstoff ist.
     
    6. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, wobei der Düngerstabilisator N-C1-6-Alkylthiophosphortriamid ist und das Alkyl Propyl oder Butyl ist.
     
    7. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, die ferner Glykole, die nicht die Glykolether aus Formel 1 sind, beinhaltet.
     
    8. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, die mindestens zwei der Eigenschaften von Dampfdruck, Flammpunkt, Viskosität, Hydroxylzahl und VOC-Gehalt aufweist.
     
    9. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, die mindestens drei der Eigenschaften von Dampfdruck, Flammpunkt, Viskosität, Hydroxylzahl und VOC-Gehalt aufweist.
     
    10. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, die mindestens vier der Eigenschaften von Dampfdruck, Flammpunkt, Viskosität, Hydroxylzahl und VOC-Gehalt aufweist.
     
    11. Düngerstabilisatorzusammensetzung gemäß Anspruch 1, die alle fünf der Eigenschaften von Dampfdruck, Flammpunkt, Viskosität, Hydroxylzahl und VOC-Gehalt aufweist.
     
    12. Eine Düngerzusammensetzung, die Folgendes beinhaltet:

    (A) die Düngerstabilisatorzusammensetzung gemäß Anspruch 1, und

    (B) einen auf Stickstoff basierten Dünger.


     
    13. Düngerzusammensetzung gemäß Anspruch 12, wobei der auf Stickstoff basierte Dünger mindestens einer von Harnstoff, Harnstoffammoniumnitrat, Ammonium und Dung ist.
     
    14. Düngerzusammensetzung gemäß Anspruch 12, wobei die Düngerstabilisatorzusammensetzung, bezogen auf das Gewicht des auf Stickstoff basierten Düngers, zwischen 0,01 und 10 Gew.-% der Düngerzusammensetzung beinhaltet.
     


    Revendications

    1. Une composition de stabilisateur d'engrais comprenant :

    (A) deux éthers de glycol ou plus de la Formule 1

    chaque élément parmi R1 et R3 est indépendamment de l'hydrogène ou du phényle à la condition que R1 et R3 ne soient pas simultanément de l'hydrogène,

    n est un nombre entier de 3 à 10, et

    R2 est de 90 à 100 % d'hydrogène ou de 0 à 10 % d'un ou de plusieurs éléments parmi du méthyle, de l'éthyle ou du phényle ; et

    (B) au moins un stabilisateur d'engrais comprenant un N-alkyl en C1-6 thiophosphorique triamide ;

    la composition de stabilisateur d'engrais étant caractérisée comme ayant au moins une propriété parmi les propriétés suivantes :

    (1) une pression de vapeur inférieure ou égale à (≤) 1 000 Pascals (Pa) à 20 °C telle que mesurée par l'ASTM E1719,

    (2) un point d'éclair égal ou supérieur à (≥) 200 °F (93 °C) tel que mesuré par l'ASTM D3278,

    (3) une viscosité inférieure ou égale à (≤) 200 centipoises (cP) à 25 °C telle que mesurée par l'ASTM D445,

    (4) un indice d'hydroxyle allant de 100 à 1 000 tel que mesuré par l'ASTM D4274, et

    (5) une teneur en COV inférieure ou égale à (≤) 50 pour cent en poids (% en poids) telle que mesurée par l'ASTM D6886.


     
    2. La composition de stabilisateur d'engrais de la revendication 1 dans laquelle l'au moins un stabilisateur d'engrais est le N-butyl thiophosphorique triamide (NBPT).
     
    3. La composition de stabilisateur d'engrais de la revendication 1 comprenant de 40 à 99,99 % en poids des deux éthers de glycol ou plus de la Formule 1, et de 0,01 à 60 % en poids du stabilisateur d'engrais.
     
    4. La composition de stabilisateur d'engrais de la revendication 1 dans laquelle R1 de la Formule 1 est de l'hydrogène et R3 de la Formule 1 est du phényle.
     
    5. La composition de stabilisateur d'engrais de la revendication 1 dans laquelle R1 de la Formule 1 est du phényle et R3 de la Formule 1 est de l'hydrogène.
     
    6. La composition de stabilisateur d'engrais de la revendication 1 dans laquelle le stabilisateur d'engrais est le N-alkyl en C1-6 thiophosphorique triamide, et l'alkyle est le propyle ou le butyle.
     
    7. La composition de stabilisateur d'engrais de la revendication 1 comprenant en sus des glycols autres que les éthers de glycol de la Formule 1.
     
    8. La composition de stabilisateur d'engrais de la revendication 1 ayant au moins deux propriétés parmi les propriétés de pression de vapeur, de point d'éclair, de viscosité, d'indice d'hydroxyle et de teneur en COV.
     
    9. La composition de stabilisateur d'engrais de la revendication 1 ayant au moins trois propriétés parmi les propriétés de pression de vapeur, de point d'éclair, de viscosité, d'indice d'hydroxyle et de teneur en COV.
     
    10. La composition de stabilisateur d'engrais de la revendication 1 ayant au moins quatre propriétés parmi les propriétés de pression de vapeur, de point d'éclair, de viscosité, d'indice d'hydroxyle et de teneur en COV.
     
    11. La composition de stabilisateur d'engrais de la revendication 1 ayant l'ensemble des cinq propriétés parmi les propriétés de pression de vapeur, de point d'éclair, de viscosité, d'indice d'hydroxyle et de teneur en COV.
     
    12. Une composition d'engrais comprenant :

    (A) la composition de stabilisateur d'engrais de la revendication 1, et

    (B) un engrais à base d'azote.


     
    13. La composition d'engrais de la revendication 12 dans laquelle l'engrais à base d'azote est au moins un engrais parmi de l'urée, de l'urée-nitrate d'ammonium, de l'ammoniac et du fumier.
     
    14. La composition d'engrais de la revendication 12 dans laquelle la composition de stabilisateur d'engrais représente entre 0,01 et 10 % en poids de la composition d'engrais rapporté au poids de l'engrais à base d'azote.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description