Note: Descriptions are shown in the official language in which they were submitted.
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NON-CORROSIVE NITRIFICATION INHIBITOR POLAR SOLVENT
FORMULATION
RELATED APPLICATIONS
[0001] This application claims benefit of U.S. Serial No. 62/244,901,
filed October
22, 2015; U.S. Serial No. 62/244,902,filed October 22, 2015; and U.S. Serial
No. 62/244,903,
filed October 22, 2015, the entire contents of which are incorporated herein
by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to relatively non-corrosive, high
load nitrapyrin
liquid formulations, comprising polar solvents and novel metal corrosion
inhibitors and
method of preparing and using the same.
BACKGROUND AND SUMMARY
[0003] (Trichloromethyl)pyridine compounds, such as nitrapyrin (2-chloro-
6-
(trichloromethyl)pyridine), inhibit the process of nitrification and have been
or are currently
used in combination with nitrogen based fertilizers as described in U.S.
3,135,594, which is
herein incorporated by reference. The application of these compounds helps to
maintain
levels of ammonium nitrogen applied to the soil in the ammonium form (plant
accessible
stabilized nitrogen); higher levels of plant accessible nitrogen in the soil
enhances crop
performance and can increase crop yields.
[0004] Due to their volatile nature some formulations of nitrapyrin, also
referred to
herein as liquid inhibitor compositions, are best applied by incorporating
them mechanically
into the soil, or by watering them into the soil within about 8 hours after
applying them to the
surface of the soil. Some encapsulated formulations of nitrapyrin are suitable
for rapid or
dump release of nitrapyrin into the soil. Some formulations of nitrapyrin
encapsulated with
lignin sulfonates, especially useful for quick release applications, are
disclosed in U.S.
4,746,513, which is incorporated herein by reference. Polycondensation
encapsulation, as
disclosed in U.S. 5,925,464, has also been used to encapsulate agriculturally
active
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ingredients such as nitrapyrin, particularly to enhance handling safety and
storage stability of
the active ingredient by using polyurethane rather than polyurea encapsulants.
[0005] Encapsulated nitrapyrin formulations exhibit certain advantages
over liquid
non-encapsulated formulations of nitrapyrin, such as improved stability.
Despite the
advantages of encapsulated nitrapyrin formulations, liquid non-encapsulated
formulations of
nitrapyrin are still used, at least in part, because they tend to be easier to
formulate and may
cost less than encapsulated nitrapyrin formulations. As with most any soil
amendment there
is an advantage to using formulations that include a high level of the
agriculturally active
component of the formulation. Formulations that have higher levels of an
active ingredient
generally mean that less material must be moved, stored, and applied to the
field; the net
result is that these formulations may exhibit lower material handling costs.
[0006] In most commercially available liquid formulations the level of
nitrapyrin has
been limited by the need to pair nitrapyrin with relatively non-corrosive
solvents. Some
aspects of the present invention provide a liquid formulation of nitrapyrin
(i.e., a liquid
inhibitor composition) that includes a relatively high level of nitrapyrin. In
these inventive
formulations nitrapyrin is present in polar solvents and is especially
formulated to be non-
corrosive or at least less corrosive than previous formulations of nitrapyrin
that included
significant levels of polar solvents. Dibasic ester, as used herein, refers to
a compound
containing two ester groups. Examples of dibasic esters include, but are not
limited to,
dimethyl glutarate, dimethyl succinate, dimethyl adipate, dimethyl 2-
methylglutarate, and
mixtures thereof
[0007] Some embodiments include a liquid formulation of nitrapyrin
comprising of:
nitrapyrin, at least one polar solvent selected from the group consisting of:
(1) N,N-dialkyl
fatty acid amides such as those found in products such as, but not limited to,
di-substituted
amides including for example N, N-dimethylocotanamide (N,N-
dimethylcarprylamide) and
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dimethyldecanamide (N,N-dimethylcapramide), compounds sold under the trade
names,
Hallcomid M810, Hallcomid M10, still other compounds that can be used in
capacity include,
for example, Rhodiasolv ADMA 810, Rhodiasolv ADMA 10, Genagen 4166 and
Genagen 4296; (2) cyclohexanone; (3) dibasic esters such as, but not limited
to, dimethyl
2-methylglutarate, which is available as Rhodiasolv IRIS; and a dibasic ester
mixture
composed of dimethyl glutarate, dimethyl succinate, and dimethyl adipate which
is available
as Rhodiasolv RPDE; (4) glycol ethers and polyalkylene diglycol ethers such
as, but not
limited to, dipropylene glycol methyl ether which is available as DowanolTM
DPM; (5)
alkylene carbonates such as, but not limited to, propylene carbonate which is
available as
Jeffsol AG 1555; (6) methyl-5-(dimethylamino)-2-methy1-5-oxopentanoate which
is
available as Rhodiasolv Polarclean; (7) organophosphate compounds such as,
but not
limited to, trialkyl phosphates, (8) alkoxybenzene compounds such as, but not
limited to,
methoxybenzene (anisole) and ethoxybenzene, (9) ketones such as, but not
limited to,
cyclopentanone and cyclohexanone, and at least one inhibitor of metal
corrosion. The liquid
formulations of the present invention may include high levels of nitrapyrin
and exhibit
relatively non-corrosive properties, making them suitable for use with metal
objects such as
metal storage tanks and metal application equipment. In one embodiment, the
alkoxybenzene
compound is methoxybenzene (anisole). In one embodiment, the organophosphate
compound
is triethyl phosphate.
[0008] In one embodiment, the corrosion inhibitor is selected from the
group
consisting of: nicotinamide, a-picoline, 2,6 lutidine, expoxidized linseed oil
(ELO) and DER
331 liquid epoxy resin.
[0009] In one embodiment, the corrosion inhibitor is niacin, also known
as nicotinic
acid. In another embodiment, the corrosion inhibitor is a niacin-derivative.
In yet another
embodiment, the corrosion inhibitor is niacinamide (it is understood that the
terms
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"niacinamide" and "nicotinamide" are synonymous), methyl isonicotinate, niacin
esters,
acipimox, aluminum nicotinate, niceritrol, nicoclonate, nicomol, inositol
hexaniacinate,
oxiniacic acid or combinations thereof.
[0010] Non-
limiting examples of niacin derivatives include methyl isonicotinate,
niacin esters, niacinamide salicylate, niacinamide ascorbate, niacinamide
folate, niacinamide
lipoate, niacinamide lactate, niacinamide glycolate, niacinamide mandalate,
niacinamide
malate, niacinamide hydroxycitrate, niacinamide hydroxytetronate, niacinamide
aleurate,
niacinamide petroselinate, niacinamide pantothenate, niacinamide adenosine
monophosphate
(AMP), niacinamide diphosphate (ADP), niacinamide adenosine triphosphate
(ATP),
niacinamide hydroquinone carboxylate, nicotinic acid, niacinamide, Acipimox (5-
methylpyrazinec arboxylic acid, 4-oxide),
aluminum nicotinate, Niceritrol (3-
pyridinecarboxylic acid 2,2-bis[[3-pyridinylcarbonyl]oxy]methyl)-1,3-
propanediy1 ester,
Nicoclonate, Nicomol (2,2 ,6,6-(1-hydroxycyclohexyl)
tetramethyltetrakis (3-
pyridinecarboxylate), inositol hexaniacinate, and Oxiniacic Acid (3-
pyridinecarboxylic acid,
1-oxide.
[0011] In
another embodiment, the corrosion inhibitor is derivatized linseed oil,
including but not limited to epoxidized linseed oil. In another embodiment,
the corrosion
inhibitor is a 1,2-epoxyalkane such as 1,2-epoxydecane. In another embodiment,
the
corrosion inhibitor is an amino alcohol, for example, 2-amino-2-methyl-1-
propanol (i.e.,
AMP-95 or AMP-99). In another embodiment, the corrosion inhibitor is an
imidazole
compound, for example, 1-methylimidazole. In another embodiment, the polar
solvent is
diethylene glycol butyl ether (DGBE),In another embodiment, the corrosion
inhibitor and/or
co-solvent is an esteramide compound.
[0012] In
yet another embodiment, the corrosion inhibitor is selected from
niacinamide, methyl isonicotinate, niacin esters, acipimox, aluminum
nicotinate, niceritrol,
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nicoclonate, nicomol, inositol hexaniacinate, oxiniacic acid, derivatized
linseed oil, including
but not limited to epoxidized linseed oil, 1,2-epoxydecane, an amino alcohol,
for example, 2-
amino-2-methyl- 1-propanol, 1-methylimidazole, a quinolone compound such as
quinaldine,
or any combination thereof.
[0013] In another aspect, described herein are liquid fertilizer
compositions for use in
agricultural applications comprising: one more nitrogenous fertilizer
compounds; at least one
nitrification inhibitor comprising a (trichloromethyl)pyridine compound; a
polar solvent; and,
optionally, a corrosion inhibitor.
[0014] In one embodiment, the liquid inhibitor composition or liquid
fertilizer
composition further comprises at least one additional component including, but
not limited to,
a co-solvent, a pH adjustor, flow agents, preservatives, buffering agents,
antifoam agents,
compatibility agents, deposition agents, dispersants, drift control agents,
penetrants,
surfactants, spreaders, and wetting agents, and the like. In one embodiment,
the nitrogenous
fertilizer compound is anhydrous ammonia.
[0015] Polar solvents that can be used to practice some embodiment of the
invention
include, but are not limited to, cyclohexanone, propylene carbonate, N,N-
dialkyl fatty acid
amides: specifically the mixture of C8/C10 fatty acid N,N-dimethylamides
(Hallcomid
M810), other fatty acid amides also C8 & C10 N,N-dimethylamides individually,
the dibasic
ester mixture composed of dimethyl glutarate, dimethyl succinate, and dimethyl
adipate
(Rhodiasolv0 RPDE), organophosphate compounds which are trialkyl phosphates,
and
alkoxybenzene compounds such as methoxybenzene (anisole) and ethoxybenzene. In
one
embodiment, the organophosphate compound may be selected from the group
including
triethyl phosphate, tri(isobutyl)phosphate, tributoxyethyl phosphate (TBEP)
and tris(2-
ethylhexyl) phosphate. In one embodiment, the polar solvent is comprised of
the dibasic ester
mixture composed of dimethyl glutarate, dimethyl succinate, and dimethyl
adipate
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(Rhodiasolv RPDE) and cyclohexanone. In one embodiment, the alkoxybenzene
compound
is methoxybenzene (anisole).
[0016]
Polar solvents that have not worked in some of the exemplary formulations
disclosed herein include; (1) dipropylene glycol monomethyl ether (Dowanol
DPM), (2)
methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate (Polarclean), and N-
butylpyrrolidone
(TamiS olve NxG).
100171
Corrosion inhibitors that may not be well suited, or even efficacious, for the
practice of the instant invention include, methyltrioctyl ammonium chloride,
poly(12-hydroxyoctadecanoic acid-co-ethylenimine) (e.g., Atlox LP6).
100181
Corrosion inhibitors that may be used to practice some embodiments of the
invention include, for example, pyridinecarboxamides (i.e., nicotinamide or
niacinamide),
methylpyridines (i.e., a-picoline, 2,6-lutidine), epoxidized seed or vegetable
oils (i.e.,
epoxidized linseed oil (ELO), epoxidized soybean oil, etc.) and epoxy resin
(liquid reaction
product of epichlorohydrin and bisphenol, such as, D.E.R.TM 331TM liquid epoxy
resin (DER
331)).
100191 A
first set of embodiments include a formulation, comprising: 2-chloro-6-
(trichloromethyl)pyridine, wherein the 2-chloro-6 (trichloromethyl)pyridine is
present in the
formulation in the range of about 200 to about 400 g/L; at least one polar
solvent, selected
from the group consisting of: a
mixture of N, N-dimethyloctanamide (N, N-
dimethylcaprylamide) and N, N-dimethyldecanamide (N, N-dimethylcapramide); a
ketone,
and a dibasic ester, wherein the polar solvent comprises between about 40 to
about 70 weight
percent of the solvent system of the formulation; at least one polar solvent
miscible corrosion
inhibitor, selected from the group consisting of: a liquid epoxy resin; 2, 6-
dimethylpyridine;
epoxidized linseed oil; and nicotinamide; wherein said polar solvent miscible
corrosion
inhibitor, comprises about 0.5 to about 2.5 weight percent; and at least one
optional second
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solvent selected from the group consisting of: solvent naphtha, an aromatic
solvent, a
mineral oil, kerosene, and xylene, wherein the second solvent comprises about
5.0 to about
20.0 weight percent of the formulation.
[0020] A second set of embodiments includes a formulation comprising:
about 240 to
about 350 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40 to about 60
weight percent
of a mixture of N, N-dimethyloctanamide (N, N-dimethylcaprylamide) and
N,N-dimethyldecanamide (N, N-dimethylcapramide); about 0.5 to about 1.5 weight
percent
of liquid epoxy resin and about 0.5 to about 1.5 weight percent 2, 6-
dimethylpyridine; and
about 5 to about 20 weight percent solvent naphtha.
[0021] A third set of embodiments includes a formulation comprising:
about 230 to
about 300 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 45 to about 55
weight percent
of a mixture of N, N-dimethyloctanamide (N, N-dimethylcaprylamide) and
N,N-dimethyldecanamide (N, N-dimethylcapramide); about 0.75 to about 1.4
weight percent
of liquid epoxy resin; about 0.5 to about 1.5 weight percent 2, 6-
dimethylpyridine; and about
to about 15 weight percent solvent naphtha.
[0022] A fourth set of embodiments includes a formulation comprising:
about 240
g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.0 to about 55 weight
percent of a
mixture of N,N-dimethyloctanamide (N,N-dimethylcaprylamide) and N, N-
dimethyldecanamide (N,N-dimethylcapramide); about 1.0 to about 1.1 weight
percent of
liquid epoxy resin oil; about 0.5 to about 1.5 weight percent 2, 6-
dimethylpyridine; and about
11.0 to about 14.0 weight percent solvent naphtha.
[0023] A fifth set of embodiments includes a formulation comprising:
about 240 g/L
of 2-chloro-6-(trichloromethyl)pyridine; about 50.55 weight percent of a
mixture of
N,N-dimethyloctanamide (N,N-dimethylcaprylamide) and N,N-dimethyldecanamide
(N,N-dimethylcapramide); about 1. 2 weight percent of liquid epoxy resin oil;
about 0.5 to
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about 1.5 weight percent 2,6-dimethylpyridine; and about 12.64 weight percent
solvent
naphtha.
[0024] A sixth set of embodiments includes a formulation comprising: about
200 to
about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 20 to about 50
weight percent
of a dibasic ester; about 0.5 to about 2.5 weight percent of epoxidized
linseed oil; about 0.5 to
about 2.5 weight percent nicotinamide; and about 20.0 to about 50.0 weight
percent
cyclohexanone.
[0025] A seventh set of embodiments includes a formulation comprising:
about 240
g/L to about 350 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 45 to
about 55 weight
percent of a dibasic ester; about 1.0 to about 2.0 weight percent of
epoxidized linseed oil; and
about 0.8 weight percent nicotinamide; and about 11.0 to about 14.0 weight
percent
cyclohexanone.
[0026] An eighth set of embodiments includes a formulation comprising:
about 240
g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.47 weight percent of a
dibasic ester;
about 1.5 weight percent of epoxidized linseed oil; about 0.8 weight percent
nicotinamide;
and about 12.62 weight percent cyclohexanone.
[0027] A ninth set of embodiments includes a formulation, comprising:
about 200 to
about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40 to about 60
weight percent
of a dibasic ester; about 0.5 to about 2.5 weight percent of epoxidized
linseed oil; and about
0.4 to about 1.5 weight percent nicotinamide.
[0028] A tenth set of embodiments include the twelfth embodiment: about
240 g/L of
2-chloro-6-(trichloromethyl)pyridine; about 63.08 weight percent of a dibasic
ester; about
1.5 weight percent of epoxidized linseed oil; and about 0.6 to about 1.0
weight percent
nicotinamide.
[0029] An eleventh set of embodiments include a formulation, comprising:
about
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240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 63.08 weight percent of
a dibasic
ester; about 1.5 weight percent of epoxidized linseed oil; and about 0.8
weight percent
nicotinamide.
[0030] A
twelfth set of embodiments includes a formulation, comprising: about 200
to about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40 to about 70
weight
percent of triethyl phosphate; about 0.5 to about 2.5 weight percent of
epoxidized linseed oil;
and about 0.5 to about 2.5 weight percent of methyl nicotinate.
[0031] A
thirteenth set of embodiments includes a formulation, comprising: about
200 to about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40 to
about 70 weight
percent of methoxybenzene; about 0.5 to about 2.5 weight percent of
nicotinamide; and about
0.5 to about 2.5 weight percent of 2-amino-2-methyl-1-propanol.
[0032] A
fourteenth set of embodiments including at least one of the formulations
according to any of the first through the thirteenth set of embodiments and at
least one
additional agricultural ingredient selected from the group consisting of:
herbicides,
insecticides, miticides, fungicides, and fertilizers.
[0033] A
fifteenth set of embodiments including any of the formulations according to
the fourteenth set of embodiments, wherein the agricultural ingredient is a
fertilizer.
[0034] A
sixteenth set of embodiments including any of the formulations according to
the formulation of the fifteenth set of embodiments, wherein the fertilizer
includes nitrogen.
[0035] A
seventeenth set of embodiments including methods for treating soil,
comprising the steps of: applying at least one of the formulations according
to the first
through sixteenth set embodiments to at least one area selected from the area
consisting of:
the surface of a portion of soil, beneath the surface of a portion of soil, a
portion of a plant,
and a portion of a surface adjacent to a plant.
[0036] The
eighteenth set of embodiments including the any of the methods
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according to the seventeenth set of embodiments, wherein the applying step
includes
injecting at least one of the formulations into a portion of soil.
DETAILED DESCRIPTION
[0037] For the purposes of promoting an understanding of the principles
of the novel
technology, reference will now be made to the preferred embodiments thereof,
and specific
language will be used to describe the same. It will nevertheless be understood
that no
limitation of the scope of the novel technology is thereby intended, such
alterations,
modifications, and further applications of the principles of the novel
technology being
contemplated as would normally occur to one skilled in the art to which the
novel technology
relates are within the scope of this disclosure and the claims.
[0038] Unless noted otherwise as used herein the term 'about' refers to a
range of
values from less than 10 percent to greater than 10 percent of the stated
value, for example
about 1.0 encompasses values from 0.9 to 1.1.
[0039] (Trichloromethyl)pyridine compounds useful in the composition of
the present
invention include compounds having a pyridine ring which is substituted with
at least one
trichloromethyl group and mineral acid salts of these compounds thereof The
presence of a
(trichloromethyl)pyridine compound suppresses the nitrification of ammonium
nitrogen in
the soil or growth medium, thereby preventing the rapid loss of ammonium
nitrogen
originating from nitrogen fertilizers, organic nitrogen constituents, or
organic fertilizers and
the like. Suitable compounds include those containing chlorine or methyl
substituents on the
pyridine ring in addition to a trichloromethyl group, and are inclusive of
chlorination
products of methyl pyridines such as the lutidines, the collidines and the
picolines. Suitable
salts of the (trichloromethyl)pyridine compounds include hydrochlorides,
nitrates, sulfates
and phosphates.
[0040] The (trichloromethyl)pyridine compounds useful in the practice of
the present
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invention are typically oily liquids or crystalline solids dissolved in a
solvent. Other suitable
compounds are described in U.S. 3,135,594. A preferred
(trichloromethyl)pyridine is
2-chloro-6-(trichloromethyl)pyridine, also known as nitrapyrin, and the active
ingredient of
the product N-SERVETM (Trademark of Dow AgroSciences LLC).
[0041] NSERVETM has an active nitrapyrin loading level of about 240 g/L.
The
nitrapyrin loading level of NSERVETM is set in part by the solubility of
nitrapyrin in the
solvents used in the formulation (e.g., Aromatic 100) and its corrosiveness at
elevated
temperature (i.e., 50 C). Still other non-polar hydrophobic solvents which can
be used in
relatively non-corrosive formulations of nitrapyrin include, but are not
limited to, other
naphthalene depleted solvents, i.e., aromatic solvent that includes less than
about
1% naphthalene. Some non-ionic, hydrophobic post-added solvents that can be
used to
prepare liquid formulations of nitrapyrin include, but are not limited to:
Aromatic 100 Fluid,
also known as solvent naphtha or light aromatic; Aromatic 150 Fluid, also
known as solvent
naphtha, heavy aromatic, high flash aromatic naphtha type II, heavy aromatic
solvent
naphtha, hydrocarbons, C10 aromatics, >1% naphthalene, A150, S150; and
Aromatic 200
Fluid, also known as solvent naphtha, heavy aromatic, high flash aromatic
naphtha type II,
heavy aromatic solvent naphtha, hydrocarbons, C10-13 aromatics, >1%
naphthalene, A200,
and S200.
[0042] Nitrapyrin tends to be more soluble in polar solvents than in non-
polar
solvents. Unfortunately, formulations of nitrapyrin in polar solvents tend to
be corrosive,
especially towards carbon steel storage containers. Due at least in part to
their corrosive
properties, formulations of nitrapyrin in polar solvents have proved to be
difficult to
commercialize. Some aspects of the present invention include identifying and
using
especially useful corrosion inhibition additives which make practical liquid
formulations of
nitrapyrin in polar solvent that include on the order of about 200 to about
400 g/L of
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nitrapyrin. These inventive formulations are markedly less corrosive than are
currently
available nitrapyrin polar solvent formulations.
[0043] In
one embodiment, the (trichloromethyl)pyridine compound is nitrapyrin.
The (trichloromethyl)pyridine compound is present in the liquid inhibitor
composition at a
lower range of 2% by weight of the composition, or in other embodiments, at a
lower range
of 3% by weight of the composition, or in other embodiments, at a lower range
of 5% by
weight of the composition.
[0044] In
another embodiment, the (trichloromethyl)pyridine compound is present in
the liquid inhibitor composition at a lower range 0.5%, or 1%, or 2%, or 3%,
or 4%, or 5%,
6%, or 8%, or 10% or 12 % or 14%, by weight of the composition. In another
embodiment,
the (trichloromethyl)pyridine compound is present in the liquid inhibitor
composition at an
upper range of 75%, or 65%, or 60% by weight of the composition. In another
embodiment,
the (trichloromethyl)pyridine compound is present in the liquid inhibitor
composition at an
upper range of 60% by weight of the composition. In another embodiment, the
(trichloromethyl)pyridine compound is present in the liquid inhibitor
composition at an upper
range of 55% by weight of the composition. In
another embodiment, the
(trichloromethyl)pyridine compound is present in the liquid inhibitor
composition at an upper
range of 59%, or 57%, or 55% or 53 % or 50%, by weight of the composition. In
another
embodiment, the (trichloromethyl)pyridine compound is present in the liquid
inhibitor
composition at an upper range of 48%, or 46%, or 45% or 42 % or 40%, by weight
of the
composition.
[0045]
Described herein are high load compositions (in one embodiment, a loading
level of 360g/L) of nitrapyrin, which demonstrate stability in various extreme
conditions,
such as cold conditions. The compositions as described herein are also capable
of provide
corrosion resistance to carbon steel tanks.
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[0046] In one embodiment, the (trichloromethyl)pyridine compound is
dispersed in
the liquid inhibitor composition at loading level of at least 200 g/L, or in
another
embodiment, at least 250 g/L, or in another embodiment, at least 300 g/L, or
in another
embodiment, at least 320 g/L, or in a further embodiment, at least 340 g/L, or
in another
embodiment, at least 360 g/L, or in yet another embodiment, at least 380 g/L,
or in another
embodiment, at least 400 g/L.
[0047] In one embodiment, the (trichloromethyl)pyridine compound,
typically 2-
chloro-6-(trichloromethyl)pyridine, has a solubility at 25 C of at least 300
grams per liter
(g/L), or in another embodiment, at least 320 g/L, or in a further embodiment,
at least 340
g/L, or in another embodiment, at least 360 g/L, or in yet another embodiment,
at least 380
g/L, or in another embodiment, at least 400 g/L.
[0048] In one embodiment, the liquid inhibitor composition are made by
contacting
one or more nitrification inhibitors with a solvent comprising at least one
organophosphate
compound, whereby the nitrification inhibitor is dissolved or dispersed in the
solvent. The
liquid inhibitor composition can further comprises at least one additional
component,
typically a corrosion inhibitor.
[0049] The liquid fertilizer compositions, as described herein, comprise:
one more
nitrogenous fertilizer compounds; at least one nitrification inhibitor
comprising a
(trichloromethyl)pyridine compound; a solvent comprising an organophosphate
compound;
and, optionally, a corrosion inhibitor. In one embodiment, the liquid
inhibitor composition
further comprises at least one additional component including, but not limited
to, a co-
solvent, a pH adjustor, flow agents, preservatives, buffering agents, antifoam
agents,
compatibility agents, deposition agents, dispersants, drift control agents,
penetrants,
surfactants, spreaders, and wetting agents, and the like.
[0050] In one embodiment, the nitrogenous fertilizer compound is anhydrous
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ammonia.
[0051] In yet another aspect, described herein are liquid fertilizer
compositions
comprising, based on weight of the composition: (a) up to about 99 wt%, by
weight of
composition, of one or more nitrogenous fertilizer compounds, which in one
embodiment is
anhydrous ammonia (b) a (trichloromethyl)pyridine compound, which in one
embodiment is
2-chloro-6-(trichloromethyl)pyridine, (c) a solvent comprising an
organophosphate
compound, and (d) a corrosion inhibitor. In one embodiment, the
organophosphate
compound is an alkyl phosphate. In one embodiment, the organophosphate
compound is
triethyl phosphate. In one embodiment, the organophosphate compound is
triethyl
phosphate, tri(isobutyl)phosphate, tributoxyethyl phosphate (TBEP) or tris(2-
ethylhexyl)
phosphate.
[0052] Methods of making a liquid fertilizer composition comprising
contacting one
or more nitrogenous fertilizer compounds with a liquid inhibitor composition,
as described
herein. In one embodiment, the nitrogenous fertilizer compound is anhydrous
ammonia. The
liquid inhibitor composition comprises, in one embodiment, at least one of a
nitrification
inhibitor, which is dissolved or dispersed in a solvent comprising at least
one
organophosphate compound. In one embodiment, the nitrification inhibitor
comprises a
(trichloromethyl)pyridine compound. The liquid inhibitor composition, in one
embodiment,
further comprises at least one additional component, typically a corrosion
inhibitor.
[0053] In one embodiment, the liquid fertilizer compositions as described
herein are
utilized for treating soil. The term "treating" in one embodiment means
contacting the
compositions as described herein with soil. The term "treating", in yet
another embodiment,
means concurrent mechanical mixing of the described compositions with soil. In
another
embodiment, the term "treating" means applying the described compositions to
the surface of
the soil and thereafter mechanically incorporating the compositions into soil
(for example, at
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a certain depth). In yet another embodiment, the term "treating" means
incorporating the
described compositions into the soil at a certain depth, such as by injection
and irrigation.
[0054] In one embodiment, the term "treating" means injecting the liquid
fertilizer
composition as described herein into soil at a depth of less than or equal to
10 inches. In
another embodiment, the term "treating" means injecting the liquid fertilizer
composition as
described herein into soil at a depth of less than or equal to 9 inches, or in
some
embodiments, less than or equal to 8 inches, or in some embodiments, less than
or equal to 7
inches, or in some embodiments, less than or equal to 6 inches, or in some
embodiments, less
than or equal to 5 inches, or in some embodiments, less than or equal to 4
inches, or in some
embodiments, less than or equal to 3 inches.
[0055] In another aspect, described herein are methods for fertilizing
target plants,
comprising applying a liquid fertilizer composition to soil or environment of
a target plant,
the liquid fertilizer composition comprising: one more nitrogenous fertilizer
compounds; at
least one nitrification inhibitor comprising a (trichloromethyl)pyridine
compound; a solvent
comprising an organophosphate compound, and, optionally, a corrosion
inhibitor. In one
embodiment, the liquid inhibitor composition further comprises at least one
additional
component including, but not limited to, a co-solvent, a pH adjustor, flow
agents,
preservatives, buffering agents, antifoam agents, compatibility agents,
deposition agents,
dispersants, drift control agents, penetrants, surfactants, spreaders, and
wetting agents, and
the like. In one embodiment, the nitrogenous fertilizer compound is anhydrous
ammonia.
[0056] In one embodiment, the liquid inhibitor composition or liquid
fertilizer
composition, as described herein, forms a stable composition at temperatures
less than or
equal to 10 C, or 7 C, or 5 C, or 3 C. In another embodiment, the liquid
inhibitor
composition or liquid fertilizer composition, as described herein, forms a
stable composition
at temperatures less than or equal to 0 C. In another embodiment, the liquid
inhibitor
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composition or liquid fertilizer composition, as described herein, forms a
stable composition
at temperatures less than or equal to -1 C, or -2 C, or -3 C, or -4 C, or -
5 C, or -6 C, or -7
C, or -8 C, or -9 C, or -10 C. In one embodiment, a stable composition
means that no
flocculation or crystallization is observed over a period of time.
[0057] In one embodiment, the liquid inhibitor composition or liquid
fertilizer
composition, as described herein, forms a stable composition for a period of
at least 24 hours.
In one embodiment, the liquid inhibitor composition or liquid fertilizer
composition, as
described herein, forms a stable composition for a period of at least 48
hours. In one
embodiment, the liquid inhibitor composition or liquid fertilizer composition,
as described
herein, forms a stable composition for a period of at least 1 week. In one
embodiment, the
liquid inhibitor composition or liquid fertilizer composition, as described
herein, forms a
stable composition for a period of at least 2 weeks.
[0058] In one embodiment, the compositions as described herein are stable
for at least
3 months in metal containers. In one embodiment, the compositions as described
herein are
stable for at least 2 months in metal containers at 25 C (or in some
embodiments, 50 C). In
one embodiment, the compositions as described herein are stable for at least 1
month in metal
containers at 25 C (or in some embodiments, 50 C). The metal containers can
be, in one
embodiment, carbon steel containers.
[0059] In another embodiment, compounds suitable as the organic solvent
component
of the composition and methods of the present invention form liquid, or
otherwise stable,
compositions with the nitrification inhibitor at temperatures at or greater
than -16 C, in
alternative embodiments, greater than -14 C, in other embodiments, greater
than -12 C, in
other embodiments, greater than -10 C, in further embodiments, greater than -
8 C, in other
embodiments, greater than -5 C, in other embodiments, greater than -3 C, in
other
embodiments, greater than -2 C, in other embodiments, greater than 0 C, in
other
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embodiments, greater than 2 C, in other embodiments, greater than 4 C, in
other
embodiments, greater than 5 C.
[0060] In some embodiments, at the specified temperature ranges or at
greater than a
specified temperature (as described herein), the liquid fertilizer composition
is stable,
meaning the nitrification inhibitor(s) do not react with the solvent or
solvent component
under anticipated manufacturing, storage, and use conditions. In another
embodiment, at the
specified temperature ranges or at greater than a specified temperature (as
described herein),
the liquid fertilizer composition is stable, meaning the liquid fertilizer
composition or liquid
inhibitor composition is or substantially is in one phase, i.e., no visible
crystals, no visible
precipitation, and/or no visible multiple liquid phases.
[0061] In one embodiment, the organophosphate compound is according to
formula
(I)
R3
0µµ
oI
0-R2
R1 (I),
wherein R1, R2 and R3, are each independently chosen from H, a C1-C16 alkyl
group, a Cl-
C16 alkenyl, group, a C1-C16 alkoxyalkyl group, a C7-C30 alkylarylalkyl group,
a C7-C30
arylalkyl group, or an aryl group; provided that at least one of R1, R2 or R3
is not H. In
another embodiment, R1, R2 and R3, are each independently chosen from H, a C1-
C12 alkyl
group, a C1-C12 alkenyl, group, a Cl-C12 alkoxyalkyl group, a C7-C30
alkylarylalkyl
group, a C7-C30 arylalkyl group, or an aryl group; provided that at least one
of R1, R2 or R3
is not H. In one embodiment, R1, R2 and R3, are each independently chosen from
H, a Cl-
C4 alkyl group, a C4-C8 alkyl group, a C1-C12 alkenyl, group, a C1-C4
alkoxyalkyl group, a
C7-C30 alkylarylalkyl group, a C7-C30 arylalkyl group, or an aryl group;
provided that at
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least one of R1, R2 or R3 is not H.
[0062] In
yet another embodiment, R1, R2 and R3, are each independently chosen
from a linear or branched C 1-C12 alkyl group, a linear or branched Cl-C12
alkenyl, group, a
linear or branched Cl -C12 alkoxyalkyl group, a linear or branched C7-C30
alkylarylalkyl
group, a linear or branched C7-C30 arylalkyl group, or an aryl group. In one
embodiment,
R1, R2 and R3, are each independently chosen from a Cl -C12 alkyl group, more
typically, a
C2-C8 alkyl group.
[0063] In
one embodiment, R1, R2 and R3, are each independently a Cl -C3 alkyl
group, typically an ethyl group. In another embodiment, R1, R2 and R3, are
each
independently a branched C 1 -C12 alkyl group, typically, a 2-ethylhexyl
group. In one
embodiment, R1, R2 and R3, are each independently a Cl-C12 alkoxyalkyl group,
typically a
butoxyethyl group.
[0064] The
present invention described herein will become apparent from the
following detailed description and examples, which comprises in one aspect, a
liquid
inhibitor composition for use in agricultural applications and/or liquid
fertilizer compositions
comprising: at least one nitrification inhibitor comprising a
(trichloromethyl)pyridine
compound; a polar solvent blend comprising at least two polar solvents: (i) a
dibasic ester
blend and (ii) a ketone such as cyclohexanone ; and, optionally, a corrosion
inhibitor.
[0065] In
another aspect, described herein are methods of making liquid inhibitor
compositions comprising contacting one or more nitrification inhibitors with a
polar solvent
blend comprising at least two polar solvents: (i) a dibasic ester blend and
(ii) a ketone such as
cyclohexanone, whereby the nitrification inhibitor is dissolved or dispersed
in the polar
solvent blend. In
one embodiment, the nitrification inhibitor comprises a
(trichloromethyppyridine compound. The liquid inhibitor composition, in one
embodiment,
further comprises at least one additional component, typically a corrosion
inhibitor.
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[0066] In another aspect, described herein are liquid fertilizer
compositions for use in
agricultural applications comprising: one or more nitrogenous fertilizer
compounds; at least
one nitrification inhibitor comprising a (trichloromethyl)pyridine compound; a
polar solvent
blend comprising at least two polar solvents: (i) a dibasic ester blend and
(ii) a ketone such as
cyclohexanone; and, optionally, a corrosion inhibitor.
[0067] In certain embodiments, the dibasic ester blend comprises:
a diester of formula (ha):
0
R1
R(' 0
0
(Ha);
a diester of formula (lib):
0 0
R2 .Ri
0 0
(lib); and
a diester of formula (IIc):
0
.,,0 ,. R2
R1 0
0
(IIc).
[0068] R1 and/or R2 can individually comprise a hydrocarbon having from
about 1 to
about 8 carbon atoms, typically, methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, n-butyl,
isoamyl, hexyl, heptyl or octyl.
[0069] In certain other embodiments, the dibasic ester blend comprises:
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a diester of the formula (Ma):
0
R1
R2 0
0
(Ma);
a diester of the formula (IIIb):
0 0
R2 R1
0 0
(Mb); and, optionally,
a diester of the formula (Inc):
0
, 0 R2
R1../ 0
0
(Inc).
[0070] R1 and/or R2 can individually comprise a hydrocarbon having from
about 1 to
about 8 carbon atoms, typically, methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, n-butyl,
isoamyl, hexyl, heptyl, or octyl. In such embodiments, the blend typically
comprises (by
weight of the blend) (i) from about 5% to about 30% of the diester of formula
(Ma), (ii) from
about 70% to about 95% of the diester of formula (IIIb), and (iii) from about
0% to about
10% of the diester of formula (Mc). More typically, the blend typically
comprises (by
weight of the blend): (i) from about 6% to about 12% of the diester of formula
(IIIa), (ii)
from about 86% to about 92% of the diester of formula (IIIb), and (iii) from
about 0.5% to
about 4% of the diester of formula (Mc).
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[0071] Most typically, the blend comprises (by weight of the blend): (i)
about 9% of
the diester of formula (Ma), (ii) about 89% of the diester of formula (Mb),
and (iii) about 1%
of the diester of formula (IIIc). 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.
[0072] In some embodiments, the polar solvent blend comprises (by weight
of the
solvent blend) up to 100 wt% or 99.9 wt% of the ketone. In one embodiment, the
polar
solvent blend comprises (by total weight of the polar solvent blend) up to 80
wt% of the
ketone. In one embodiment, the polar solvent blend comprises (by total weight
of the polar
solvent blend) up to 90 wt% of the ketone. In one embodiment, the polar
solvent blend
comprises (by total weight of the polar solvent blend) up to 70 wt% of the
ketone. In one
embodiment, the polar solvent blend comprises (by total weight of the polar
solvent blend) up
to 65 wt% of the ketone. In one embodiment, the polar solvent blend comprises
(by total
weight of the polar solvent blend) up to 60 wt% of the ketone. In one
embodiment, the polar
solvent blend comprises (by total weight of the polar solvent blend) up to 55
wt% of the
ketone. In one embodiment, the polar solvent blend comprises (by total weight
of the polar
solvent blend) up to 50 wt% of the ketone. In one embodiment, the polar
solvent blend
comprises (by total weight of the polar solvent blend) up to 45 wt% of the
ketone. In one
embodiment, the polar solvent blend comprises (by total weight of the polar
solvent blend) up
to 40 wt% of the ketone. It is believe that the composition of the polar
solvent blend allows
for the loading levels as described herein.
[0073] Suitable example of ketones include but are not limited to any one
or more of
acetone, methyl ethyl ketone, methyl propyl ketone, cyanoacetone, ethoxy:
acetone,
acetonylacetone, diacetone alcohol, methyl isobutyl ketone, diethyl ketone,
diisopropyl
ketone, diisobutyl ketone, methyl-n-amyl ketone, methyl-n-hexyl ketone,
cyclopentanone,
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methylcyclohexanone, methyl-cyclopentanone, cyclohexanone,
methylallylcyclohexanone,
phenylcyclohexanone, cyclohexylcyclohexanone, benzylcyclohexanone, phorone,
isophorone, and, B-ionone, methyl vinyl ketone, methyl isopropenyl ketone,
methyl propenyl
ketone, mesityl oxide, chloroacetone, acetophenone, benzophenone, methyl 2-
naphthyl
ketone, propiophenone, butyrophenone, p-acetyl biphenyl, p-methylacetophenone,
p-methoxyacetophenone, p-chloroacetophenone, p-bromoacetophenone, acetoa'cetic
ester,
acetoacetic nitrile, acetoacetic amide, acetyl-p cymene, dibenzyl ketone, and
the like. In one
embodiment, the ketone is cyclohexanone.
[0074] In some embodiments, the dibasic ester blend comprises adducts of
alcohol
and linear diacids, each adduct having the formula (IV):
R-00C-A-COO-R
(IV)
[0075] wherein R is an alkyl group (e.g., methyl, ethyl, etc.) and A is a
mixture of ¨
(CH2)4-, -(CH2)3, and ¨(CH2)2-. In other embodiments, the blend comprises
adducts of
alcohol, typically ethanol, and linear diacids, the adducts having the formula
R1-00C-A-
COO-R2, wherein at least part of R1 and/or R2 are residues of at least one
linear alcohol
having 4 carbon atoms, and/or at least one linear or branched alcohol having
at least 5 carbon
atoms, and wherein A is a divalent linear hydrocarbon. In some embodiments A
is one or a
mixture of ¨(CH2)4-, -(CH2)3, and ¨(CH2)2-. In other embodiments, the dibasic
ester
comprises adducts of an alcohol and linear or branched diacids, the adducts
having the
formula (IV): R-00C-A-COO-R, wherein R is an alkyl group (e.g., methyl, ethyl,
etc.) and
A one of the following:¨(CH2)4-, -(CH2)3, ¨(CH2)2-, ¨CH2-, or any mixture
thereof.
[0076] The dibasic ester blend may be derived from one or more by-
products in the
production of polyamide, for example, polyamide 6,6. In one embodiment, at
least one
dibasic ester comprises a blend of linear or branched, cyclic or noncyclic, Cl
C20 alkyl, aryl,
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alkylaryl or arylalkyl esters of adipic diacids, glutaric diacids, and
succinic diacids. In
another embodiment, the composition comprises a blend of linear or branched,
cyclic or
noncyclic, Cl C20 alkyl, aryl, alkylaryl or arylalkyl esters of adipic
diacids, methylglutaric
diacids, and ethylsuccinic diacids
[0077] Generally, polyamide is a copolymer prepared by a condensation
reaction
formed by reacting a diamine and a dicarboxylic acid. Specifically, polyamide
6,6 is a
copolymer prepared by a condensation reaction formed by reacting a diamine,
typically
hexamethylenediamine, with a dicarboxylic acid, typically adipic acid.
[0078] 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 diacids, and succinic diacids (herein referred to sometimes
as "AGS" or the
"AGS blend"). In one embodiment the dibasic ester blend comprises dimethyl
adipate,
dimethyl glutarate and dimethyl succinate.
[0079] 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
polyamide, typically polyamide 6,6. The composition comprises a blend of
dialkyl esters of
methylglutaric diacids, ethylsuccinic diacids, and optionally adipic diacids
(herein referred to
sometimes as "MGA", "MGN", "MGN blend" or "MGA blend"). In one embodiment the
dibasic ester blend comprises dimethyl adipate, dimethyl methylglutarate and
dimethyl
ethylsuccinate.
[0080] In one embodiment, the liquid inhibitor composition or liquid
fertilizer
composition further comprises at least one additional component including, but
not limited to,
a co-solvent, a pH adjustor, flow agents, preservatives, buffering agents,
antifoam agents,
compatibility agents, deposition agents, dispersants, drift control agents,
penetrants,
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surfactants, spreaders, and wetting agents, and the like. In one embodiment,
the nitrogenous
fertilizer compound is anhydrous ammonia.
[0081] In another aspect, described herein are methods of making a liquid
fertilizer
compositions comprising contacting one or more nitrogenous fertilizer
compounds with
liquid inhibitor composition. In one embodiment, the nitrogenous fertilizer
compound is
anhydrous ammonia. The liquid inhibitor composition comprises, in one
embodiment, at
least one of a nitrification inhibitor, which is dissolved or dispersed in a
solvent blend
comprising at least two solvents: (i) a dibasic ester blend and (ii) a ketone
such as
cyclohexanone. In one embodiment, the nitrification inhibitor comprises a
(trichloromethyl)pyridine compound. The liquid inhibitor composition, in one
embodiment,
further comprises at least one additional component, typically a corrosion
inhibitor.
[0082] In another embodiment, one or more second solvents can be used to
dissolve
or disperse (trichloromethyl)pyridine compounds at high loading levels and
include, but are
not limited to, solvent naphtha, aromatic solvents, mineral oils, kerosene,
and chlorinated
aliphatic and aromatic hydrocarbons. In one particular embodiment, the one or
more second
solvents used to dissolve or disperse (trichloromethyl)pyridine compounds at
high loading
levels include but are not limited to xylene and solvent naphtha.
[0083] In one particular embodiment, the co-solvent is an esteramide
compound
according to formula
(II): R100C-A-CONR2R3 (II)
wherein:
A is a divalent linear or branched (C2-C8)aliphatic group, and
R1 , R2, and R3 are each independently (C 1 -C 1 2)alkyl, (C1 -C 1 2)aryl, (C
1 -
C12)alkaryl or (C1-C12)arylalkyl, and R2 and R3 may each optionally be
substituted with
one or more hydroxyl groups.
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[0084] The inventive formulations of (trichloromethyl)pyridine
compound may be
applied to the soil or a growth medium at a rate in the range of at least one
lower limit
selected from the group of lower limits consisting of about 0.1., about 0.25,
about 0.5 and
about 0.58 kg/hectare to at least one upper limit selected from the group
consisting of about
1.0, about 1.2 and about 1.5 kg/hectare. The preferred amount can be easily
ascertained by
the application preference, considering factors such as soil pH, temperature,
soil type and
mode of application.
[0085] The formulation of the present invention can be applied in
any manner which
will benefit the crop of interest. In one embodiment the inventive formulation
is applied to
growth medium in a band or row application. In another embodiment, the
formulation is
applied to or throughout the growth medium prior to seeding or transplanting
the desired crop
plant. In yet another embodiment, the formulation can be applied to the root
zone of growing
plants.
[0086] The soil may be prepared in any convenient manner compatible
with the use
of the present invention, including mechanically mixing the formulation with
the soil. Still
other application may include applying the formulation to the surface of the
soil and
thereafter dragging, dicing or cutting the formulation into the soil to a
desired depth. Still
other methods of delivering the nitrification inhibitor into the soil, include
methods such as
injection, and spraying, or irrigation. In many applications the
(trichloromethyl)pyridine
compound is delivered into the soil to the desired depth of up to 6 inches
(15.24 cm.).
[0087] In some embodiments the inventive nitrapyrin formulation may
be used along
with other agriculturally active ingredients such as insecticides, fungicides,
mitocides,
herbicides, and the like.
[0088] Some exemplary herbicides which can be used along with the
inventive
nitrapyrin formulations include, but are not limited to acetochlor, alachlor,
aminopyralid,
,
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atrazine, benoxacor, bromoxynil, carfentrazone, chlorsulfuron, clodinafop,
clopyralid,
dicamba, diclofop-methyl, dimethenamid, fenoxaprop, flucarbazone, flufenacet,
flumetsulam,
flumiclorac, fluroxypyr, glufosinate-ammonium, glyphosate, halosulfuron-
methyl,
imazamethabenz, imazamox, imazapyr, imazaquin, imazethapyr, isoxaflutole,
quinclorac,
MCPA, MCP amine, MCP ester, mefenoxam, mesotrione, metolachlor, s-metolachlor,
metribuzin, metsulfuron methyl, nicosulfuron, paraquat, pendimethalin,
picloram,
primisulfuron, propoxycarbazone, prosulfuron, pyraflufen ethyl, rimsulfuron,
simazine,
sulfosulfuron, thifensulfuron, topramezone, tralkoxydim, triallate,
triasulfuron, tribenuron,
triclopyr, trifluralin, 2,4-D, 2,4-D amine, 2,4-D ester and the like, 4-CPA, 4-
CPB, 4-CPP,
2,4-D, 3,4-DA, 2,4-DB, 3,4-DB, 2,4-DEB, 2,4-DEP, 3,4-DP, 2,4,5-TB, 2,3,6-TBA,
allidochlor, acetochlor, acifluorfen, aclonifen, alachlor, alloxydim, alorac,
ametridione,
ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor,
aminopyralid,
aminopyralid, amiprofos-methyl, amitrole, anilofos, anisuron, asulam, asulam,
atraton,
atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid,
benazolin,
bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone,
benzadox,
benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop,
benzthiazuron, bicylopyrone, bifenox, bilanafos, bilanafos, bispyribac,
bromacil, bromobonil,
bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil,
butamifos,
butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate,
cafenstrole,
cafenstrole, cambendichlor, carbasulam, carbasulam, carbetamide, carboxazole
chlorprocarb,
carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl,
chlorazifop,
chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop,
chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen,
chloropon,
chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron,
chlorthal,
chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim,
cliodinate,
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clodinafop, clofop, clomazone, clomeprop, clomeprop, cloprop, cloproxydim,
clopyralid,
clopyralid, cloransulam, CPMF, CPPC, credazine, cumyluron, cyanatryn,
cyanazine,
cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat,
cyprazine,
cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham,
desmetryn, di-
allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop,
dichlorprop-P, diclofop,
diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat,
diflufenican,
diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn,
dimethenamid,
dimethenamid-P, dimexano, dimidazon, dinitramine, dinitramine, dinofenate,
dinoprop,
dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr,
diuron, DMPA,
DNOC, EBEP, eglinazine, endothal, epronaz, epronaz, EPTC, erbon, esprocarb,
ethalfluralin,
ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen,
ethoxysulfuron, etinofen,
etnipromid, etnipromid, etnipromid, etobenzanid, EXD, fenasulam, fenasulam,
fenasulam,
fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop,
fentrazamide,
fenuron, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-
P, fluazolate,
flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican,
flufenpyr, flumetsulam,
flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen,
fluoroglycofen,
fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupoxam, flupropacil,
flupropanate,
flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone,
fluthiacet, fomesafen,
fomesafen, foramsulfiiron, fosamine, furyloxyfen, glufosinate, glyphosate,
halauxifen,
halosafen, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P,
hexazinone,
imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr,
imazosulfuron,
indanofan, indaziflam, iodobonil, iodosulfuron, ioxynil, ipazine,
ipfencarbazone, iprymidam,
isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin,
isoproturon, isouron,
isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate,
ketospiradox, lactofen,
lenacil, linuron, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P,
medinoterb,
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mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam,
metamifop,
metamifop, metamitron, metazachlor, metazosulfuron, metflurazon,
methabenzthiazuron,
methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methiuron,
methometon,
methoprotryne, methyldymron, metobenzuron, metobromuron, metolachlor, S-
metolachlor,
metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron,
monochloroacetic acid, monolinuron, monuron, morfamquat, naproanilide,
napropamide,
naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen,
nitrofluorfen, norflurazon,
noniron, OCH, orbencarb, orthosulfamuron, oryzalin, oryzalin, oxadiargyl,
oxadiazon,
oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat,
pebulate,
pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone,
perfluidone,
pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron,
picloram,
picloram, picolinafen, picolinafen, pinoxaden, piperophos, pretilachlor,
primisulfuron,
procyazine, prodiamine, prodiamine, profluazol, profluralin, profoxydim,
proglinazine,
prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham,
propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin,
prosulfocarb,
prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen,
pyrasulfotole,
pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb,
pyriclor, pyridafol,
pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone,
pyroxsulam,
quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P,
rhodethanfl,
rimsulfuron, sebuthylazine, secbumeton, sethoxydim, siduron, simazine,
simeton, simetryn,
sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron,
sulglycapin, swep,
tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil,
terbucarb,
terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor,
thiazafluron,
thiazopyr and triclopyr, thidiazimin, thidiazuron, thidiazuron, thiencarbazone-
methyl,
thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim,
tri-allate,
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triasulfuron, triaziflam, tribenuron, tricamba, tridiphane, trietazine,
trifloxysulfuron,
trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine,
trimeturon, tripropindan,
tritac, tritosulfuron, vernolate, xylachlor, and compounds of the following
Formula
NH2 N H2
R X
or ArNCOOH
ArNCOOH
wherein Ar represents a phenyl group substituted with one to four substituents
independently
selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, C2-C4 alkoxyalkyl, C2-C6
alkylcarbonyl, C1-C6 alkylthio, C1-C6 haloalkyl, C1-C6 haloalkoxy, C2-C4
haloalkoxyalkyl,
C2-C6 haloalkylcarbonyl, Cl -C6 haloalkylthio, ¨OCH2CH2¨, ¨OCH2CH2CH2¨,
¨OCH20¨
or ¨OCH2CH20¨; R represents H or F; X represents Cl or vinyl; and Y represents
Cl, vinyl
or methoxy; and their salts and esters as disclosed, for example, in US7314849
B2,
US7300907 B2, US7786044 B2 and US7642220 B2. Depending upon the stability of
the
herbicide compounds used in the presence of the component of the inventive
formulation and
the preferred mode of applying the compounds these compounds may be applied
along with
the inventive nitrapyrin formulation. In many instances the compound may be
applied by any
suitable means either before or after the inventive formulation is applied to
the soil.
100891 Especially suitable herbicides useful with the compositions and
methods
described herein include 2,4-D, 2,4-DB, aminocyclopyrachlor, aminopyralid,
clopyralid,
dicamba, fluroxypyr, halauxifen, MCPA, MCPB, picloram, triclopyr, acetochlor,
atrazine,
benfluralin, cloransulam, cyhalofop, diclosulam, dithiopyr, ethalfluralin,
florasulam,
flumetsulam, glufosinate, glyphosate, haloxyfop, isoxaben, MSMA, oryzalin,
oxyfluorfen,
pendimethalin, penoxsulam, propanil, pyroxsulam, quizalofop, tebuthiuron,
trifluralin, and
the compound of the Formula.
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NH2
F CI
COOH
CI
OCH3
and its C1-C12 alkyl or C7-C12 arylalkyl ester or salt derivatives such as,
for example, the
benzyl ester.
[0090]
Some exemplary insecticides which can be used along with the inventive
nitrapyrin formulations include, but are not limited to abamectin, acephate,
acetamiprid,
acrinathrin, alpha-cypermethrin, alpha-endosulfan, azadirachtin, azinphos-
ethyl, azinphos-
methyl, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-
cypermethrin, bifenthrin,
bufencarb, buprofezin, butacarb, cadusafos, carbaryl, carbofuran, carbosulfan,
cartap, cartap
hydrochloride, chlorantraniliprole, chlorfenapyr, chlorfenvinphos,
chlorfluazuron,
chlormephos, chlorpyrifos, chlorpyrifos-methyl,
chromafenozide, clothianidin,
cyantraniliprole, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin,
diazinon, dicrotophos,
diflubenzuron, dimethoate dinotefuran, disulfoton, emamectin, emamectin
benzoate,
endosulfan, endothion, endrin, EPN, esfenvalerate, etaphos, ethiofencarb,
ethion, ethiprole,
ethoate-methyl, etofenprox, fenamiphos, fenazaflor, fenethacarb, fenitrothion,
fenobucarb,
fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil,
flonicamid,
flubendiamide, flucythrinate, fonofos, fufenozide, furathiocarb, gamma-
cyhalothrin, gamma-
HCH, halfenprox, halofenozide, heptenophos, hyquincarb, imidacloprid,
indoxacarb,
isazofos, isobenzan, isocarbophos, isofenphos, isofenphos-methyl, isoprocarb,
isothioate,
isoxathion, kinoprene, lambda-cyhalothrin, lepimectin, lufenuron, malathion,
methamidophos, methomyl, methoxyfenozide, mevinphos, mexacarbate, milbemectin,
monocrotophos, nitenpyram, novaluron, omethoate, oxamyl, oxydemeton-methyl,
oxydeprofos, oxydisulfoton, parathion, parathion-methyl, penfluron,
permethrin, phenthoate,
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phorate, phosalone, phosfolan, phosmet, phosphamidon, pirimetaphos,
pirimicarb,
pirimiphos-ethyl, pirimiphos-methyl, primidophos, profenofos, profluthrin,
promecarb,
propaphos, propoxur, prothiofos, pymetrozine, pyrafluproleõ pyridalyl,
pyrifluquinazon,
pyriprole, pyriproxyfen, spinetoram, spinosad, spirotetramat, sulfoxaflor,
sulprofos, tau-
fluvalinate, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,
tetramethylfluthrin, theta-
cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocyclam, thiocyclam
oxalate,
thiodicarb, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium,
thuringiensin,
tolfenpyrad, triazophos, triflumuron and zeta-cypermethrin. Depending upon the
stability of
the insecticide compounds used in the presence of the component of the
inventive
formulation and the preferred mode of applying the compounds these compounds
may be
applied along with the inventive nitrapyrin formulation. In many instances the
compound
may be applied by any suitable means either before or after the inventive
formulation is
applied to the soil.
[0091] Some exemplary fungicides which can be used along with the
inventive
nitrapyrin formulations include, but are not limited to tricyclazole,
phthalide, carpropamide,
pyroquilon, diclocymet, fenoxanil, probenazole, isoprothiolane, iprobenfos,
isotianil, tiadinil,
kasugamycin, flutolanil, mepronil, pencycuron, polyoxins, validamycin,
toclophos-methyl,
boscalid, penthiopyrad, thifluzamide, bixafen, fluopyram, isopyrazam,
propiconazole,
difenoconazole, fenbuconazole, ipconazole, triadimefon, hexaconazole,
azoxystrobin,
metaminostrobin, orysastrobin and acibenzolar-S-methyl. Some of these
fungicides may not
be effective for disease control when applied at the timing of application of
the inventive
formulation because fungal disease propagation and growth cycles may not be
optimal. The
effective use and application timing of these fungicides can be easily
determined by one of
normal skill in the art. Depending upon the stability of the fungicide
compounds used in the
presence of the component of the inventive formulation and the preferred mode
of applying
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the compounds these compounds may be applied along with the inventive
nitrapyrin
formulation. In many instances the compound may be applied by any suitable
means either
before or after the inventive formulation is applied to the soil.
[0092] Some exemplary herbicide safeners which can be used along with the
inventive nitrapyrin formulations include, but are not limited to benoxacor,
benthiocarb,
cloquintocet-mexyl, daimuron, dichlormid, dicyclonon, dimepiperate,
fenchlorazole-ethyl,
fenclorim, flurazole, fluxofenim, furilazole, Harpin proteins, isoxadifen-
ethyl, mefenpyr-
diethyl, mephenate, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil,
R29148
and N-phenyl-sulfonylbenzoic acid amides. Depending upon the stability of the
herbicide
safener compounds used in the presence of the component of the inventive
formulation and
the preferred mode of applying the compounds these compounds may be applied
along with
the inventive nitrapyrin formulation. In many instances the compound may be
applied by any
suitable means either before or after the inventive formulation is applied to
the soil.
[0093] Some exemplary plant growth regulators which can be used along
with the
inventive nitrapyrin formulations include, but are not limited to 2,4-D, 2,4-
DB, IAA, IBA,
naphthaleneacetamide, a-naphthaleneacetic acid, kinetin, zeatin, ethephon,
aviglycine,
1-methylcyclopropene (1-MCP), ethephon, gibberellins, gibberellic acid,
abscisic acid,
ancymidol, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole,
brassinolide,
brassinolide-ethyl and ethylene. Depending upon the stability of the plant
growth regulator
compounds used in the presence of the component of the inventive formulation
and the
preferred mode of applying the compounds these compounds may be applied along
with the
inventive nitrapyrin formulation. In many instances the compound may be
applied by any
suitable means either before or after the inventive formulation is applied to
the soil.
Exemplary Formulations
[0094] Example 1: The high load nitrapyrin SL formulations (360 g/L)
comprising
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polar solvents were prepared by dissolving nitrapyrin technical in the solvent
systems, which
included polar solvents corrosion inhibitors. The solutions were mixed under
IKA mixing
until they were essentially homogeneous.
[0095] Referring now to Table 1. All samples were tested for metal
corrosion
stability at different time intervals at 50 C temperature and compared against
N-serve
commercial control formulation. Results are shown in the Table 1. Metal
coupons (Carbon
steel (AISI 1018) were tested for corrosion stability in 40 ml prepared
nitrapyrin
formulations. Coupons were ¨45% submerged in the solution for the corrosion
testing.
Metal coupons were approximately one half inch in width and three inches in
length with a
thickness of 1/16th to 1/8th of an inch. During the testing, coupons were
visually inspected
for corrosion by checking any color changes or residue deposits on the coupon
surface. The
results of these experiments are summarized in Table 1.
[0096] Table 1: Example compositions of stable high load nitrapyrin SL
formulations (360 g/L Nitrapyrin technical) comprising polar solvents after
corrosion testing
with carbon steel coupons at 50 C. The control (N-SERVE) sample (Sample 1) has
a loading
of 240 g/L.
Nitrapyrin # of
days
Corrosion
technical
without
Sample#Solvents Inhibitor
Loadingvisible
Additives
(Wt /o)
corrosion
Aromatic 100 (66.53 wt%)
1 (Control) 24.74 ELO (0.75 wt%) 53
Xylene (7.398 wt%)
ELO (1 wt%)
2 34.6 Hallcomid M-8-10 (63.4 wt%) 2,6 Lutidine (1 67
wt%)
ELO (1 wt%)
3 34.6 Hallcomid M-8-10 (63.4 wt%) Nicotinamide (1 7
wt%)
DER331 (1.2
wt%)
4 32.9 Cyclohexanone (6439 wt%) 53
2,6 Lutidine (1
wt%)
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Nitrapyrin
Corrosion # of
days
technical
without
Sample# Solvents Inhibitor
Loadingvisible
Additives
(Wt%)
corrosion
DER331 (1.2
wt%)
34.6 Hallcomid M-8-10 (63.2 wt%)
43
2,6 Lutidine (1
wt%)
DER331 (1.2
Cyclohexanone (51.89 wt%) wt%)
46
6 32.94
Aromatic 100 (12.97 wt%) 2,6 Lutidine (1
wt%)
Hallcomid M-8-10 (50.71 ELO (1 wt%)
7 34.62 wt%) 2,6 Lutidine (1 67
Aromatic 100 (12.68 wt%) wt%)
DER331 (1.2
Hallcomid M-8-10 (50.55
wt%)
8 34.62 wt/o)2.6 Lutidine (1 >120
Aromatic 100 (12.64 wt%)
wt%)
DER331 (1.8
Cyclohexanone (51.41 wt%) wt%)
9 32.94 32
Aromatic 100 (12.85 wt%) a-picoline (1
wt%)
Hallcomid M-8-10 (50.71 ELO (1.5 wt%)
34.62 wt%) Nicotinamide 22
Aromatic 100 (12.68 wt%) (0.5 wt%)
Hallcomid M-8-10 (50.71 ELO (1.5 wt%)
11 34.62 wt%) Nicotinamide 51
Aromatic 100 (12.68 wt%) (2.5 wt%)
DER331 (1.2
Hallcomid M-8-10 (50.55
wt%)
12 34.62 wt%)
a-picoline (1 35
Aromatic 100 (12.64 wt%) wt%)
DER331 (1.8
Hallcomid M-8-10 (46.44
wt%)
13 34.29 wt%)
Nicotinamide (2 18
Aromatic 100 (15.48 wt%)
wt%)
ELO (1.5 wt%)
Hallcomid M-8-10 (61.89
14 34.29 Nicotinamide (2 30
wt%)
wt%)
RhodiaSolv RPDE (50.47 ELO (1.5 wt%)
34.62 wt%) Nicotinamide (.8 >120
Cyclohexanone (12.62 wt%) wt%)
ELO (1.5 wt%)
RhodiaSolv RPDE (63.08
16 34.62 Nicotinamide 105
wt%)
(0.8 wt%)
RhodiaSolv RPDE (63.88
17 34.62 ELO (1.5 wt%) 19
wt%)
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Nitrapyrin # of
days
Corrosion
technical
without
Sample#
Loading Solvents Inhibitor
Additives
visible
(Wt%)
corrosion
ELO (1 wt%)
RhodiaSolv PolarClean (67.10 .
18 30.90 Nicotinamide (1 4
wt%)
wt%)
ELO (1 wt%)
RhodiaSolv PolarClean (67.10
19 30.90 2,6 Lutidine (1 4
wt%)
wt%)
DER331 (1.2
RhodiaSolv RPDE (66.90 wt%)
20 30.90 4
wt%) 2,6 Lutidine (1
wt%)
DER331 (1.2
RhodiaSolv RPDE (66.90 wt%)
21 30.90 4
wt%) Nicotinamide (1
wt%)
DER331 (1.8
wt%)
22 32.94 Dowanol DPM
(62.76 wt/o)3
Nicotinamide
(2.5 wt%)
ELO (1.5 wt%)
23 33.65 Dowanol DPM (62.35 wt%) Nicotinamide 3
(2.5 wt%)
ELO (1.5 wt%)
24 34.6 TamiSolve NxG (61.40 wt%) Nicotinamide 4
(2.5 wt%)
Common chemical names of commercial available solvents found in Table 1:
Hallcomid M-
8-10: Mixture of N, N-dimethyloctanamide (N, N-dimethylcaprylamide) and
N,N-dimethyldecanamide (N, N-dimethylcapramide); RhodiaSolv RPDE: Reaction
mass of
dimethyl adipate and dimethyl glutarate and dimethyl succinate; Aromatic 100:
Solvent
Naphtha (petroleum), light aromatic; TamiSolve NxG: N-butylpyrrolidone.
[0097] Example 2: A stock solution of 360g/L nitrapyrin technical grade in
triethyl
phosphate was prepared and additives in specific amounts to limit corrosion to
carbon steel
were added to this solution. A small quantity (-15mL) of the solution in glass
jars were left
for storage stability at room temperature (¨ 20C) and -12 C. The -12C sample
was seeded
after it reached 24 hrs age by incorporating few small grains of nitrapyrin
technical in the
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cold solution and was immediately stored back to the -12 C storage
temperature. A carbon
steel coupon was partially submerged into the solution stored at 54C. The
coupon was
periodically observed for any sign of corrosion in liquid and vapor phases.
The solutions at
room temperature and -12C were observed for any inhomogeneity, crystallization
and
flowability. Table 2 shows summary of the observations.
100981 Table 2:
Composition Days Tested Coupon -12C stability
Corrosion (54C)
Stock solution (no 28 days Corroded overnight
Small amount of
additive) crystals formed
overnight
Stock (99%) +AMP-95 28 days No corrosion Homogeneous
(1%) solution
Stock (99%) + Quinaldine 28 days No corrosion Small amount of
(1%) crystals
Stock (98.5 %) + 18 days No corrosion
Small amount of
Epoxidized linseed oil crystals
(1%) + AMP 95 (0.5%)*
Stock (98.5 %) + 18 days No corrosion
Small amount of
Epoxydecane (1%) + crystals
AMP-99 (0.5%)
Stock (98.5 %) + 18 days No corrosion
Small amount of
Epoxidized linseed oil crystals
(1%) + Methyl Nicotinate
(0.5%)
Stock (98.5 %) + 18 days No corrosion
Homogeneous
Epoxydecane (1%) + solution
Methyl Nicotinate (0.5%)
[0099] Example 3: Homogeneous compositions of nitrapyrin technical grade
(360
g/L) were made in different ratios of mixture of cyclopentanone or
cyclohexanone and
Rhodiasolv RPDE (mixture of dimethyl glutarate, dimethyl adipate and dimethyl
succinate).
A small quantity (-15mL) of the solution in glass jars were left for storage
stability at room
temperature (¨ 20C) and -10C. The -10C sample was seeded after it reached 24
hrs age by
incorporating few small grains of Nitrapyrin technical in the cold solution
and was
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immediately stored back to the -10C temperature. The solutions at different
temperatures
were observed for any inhomogeneity, crystallization and flowability. No
crystals or any
other inhomogeneities were observed in the solution at any temperatures within
2 weeks of
storage. Table 3 shows a summary of the compositions and their stability.
[00100] Table 3:
Composition (360g/L Nitrapyrin Stability at room temperature and -
technical in solvent mixtures) 10C
Cylcopentanone/RPDE (60-40 wt%) Homogeneous solution
Cylcohexanone/RPDE (60-40 wt%) Homogeneous solution
Cyclopentanone Homogeneous solution
Cyclohexanone Homogeneous solution
[00101] Corrosion tests: A stock solution of 360g/L nitrapyrin technical
grade in
cyclohexanone/RPDE (60:40 weight ratio) was prepared and corrosion inhibitors
in specific
amounts were added to this solution. The resultant solutions were tested for
corrosion issues
with carbon steel tanks using following protocol. A carbon steel coupon was
partially
submerged into the solution stored at 54C. The coupon was periodically
observed for any
sign of corrosion in liquid and vapor phases. Table 4 shows a summary of the
observations.
[00102] Table 4:
Composition Coupon appearance
Stock (no corrosion inhibitor) Corrosion in liquid and vapor phase
overnight
98.5 wt% Stock + 1.0 wt% No sign of corrosion in liquid or
Epoxydecane + 0.5% vapor phase for duration of
Nicotinamide observation (45 days)
98.5 wt% Stock + 1.0 wt% No sign of corrosion in liquid or
Epoxydecane + 0.5% 1-methyl vapor phase for duration of
Imidazole observation (18 days)
97.0 wt% Stock + 1.0 wt% No sign of corrosion in liquid phase
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Nicotinamide + 2.0 wt% and slight corrosion in vapor phase
epoxidized linseed oil for duration of observation
(90 days); test conducted at 50C
[00103] Example 4: Storage stability tests : Homogeneous composition of
nitrapyrin
technical grade (360 g/L) was dispersed in methoxybenzene solvent, and a
quantity of about
15 mL of the solution in glass jars were left for storage stability at room
temperature (-- 20
C), 54 C and -7 C. The -7 C sample was seeded after it reached 24 hrs age by
incorporating
few small grains of nitrapyrin technical in the cold solution and was
immediately stored back
to the -7 C temperature. The solutions at different temperatures were observed
for any
inhomogeneity, crystallization and flowability. No crystals or any other
inhomogeneities
were observed in the solution at any temperatures within 2 weeks of storage.
[00104] Corrosion tests: A stock solution of 360 g/L nitrapyrin technical
grade in
methoxybenzene was prepared and corrosion inhibitors in specific amount were
added to this
solution. The resultant solutions were tested for corrosion issues with carbon
steel tanks using
following protocol. A carbon steel coupon was partially submerged into the
solution stored
at 54 C. The coupon was periodically observed for any sign of corrosion in
liquid and vapor
phases. Table 5 shows summary of the observations.
[00105] Table 5:
Composition Coupon appearance
Stock (no corrosion inhibitor) No sign of corrosion in liquid or
vapor
phase until 45 days; later corrosion in vapor
phase
98.5 wt% Stock + 1.0 wt% Methyl No sign of corrosion in liquid or
vapor
Isonicotinate + 0.5% AMP-95 phase for duration of observation (70
days)
99.0 wt% Stock + 0.5 wt% No sign of corrosion in liquid or
vapor
Nictotinamide + 0.5% AMP-95 phase for duration of observation (70
days)
99.0 wt% Stock + 0.5 wt% No sign of corrosion in liquid or
vapor
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Nictotinamide + 1% Epoxydecane
phase for duration of observation (24 days)
[00106] While the novel technology has been illustrated and described in
detail in the
figures and foregoing description, the same is to be considered as
illustrative and not
restrictive in character, it being understood that only the preferred
embodiments have been
shown and described and that all changes and modifications that come within
the spirit of the
novel technology are desired to be protected. As well, while the novel
technology was
illustrated using specific examples, theoretical arguments, accounts, and
illustrations, these
illustrations and the accompanying discussion should by no means be
interpreted as limiting
the technology. All patents, patent applications, and references to texts,
scientific treatises,
publications, and the like referenced in this application are incorporated
herein by reference
in their entirety.
39
