Note: Descriptions are shown in the official language in which they were submitted.
1
FORMULATIONS COMPRISING AT LEAST ONE OF METHYLGLYCINE DIACETATE,
GLUTAMIC ACID DIACETATE OR AN ALKALI METAL SALT THEREOF AND AT LEAST
ONE ORGANIC PHOSPHATE, PHOSPHONATE OR PHOSPHITE OR A SALT THEREOF,
AND THEIR USE ON THE GROUND OR PLANTS
Description
The present invention relates to the use of formulations comprising
(A) one or more aminocarboxylates, selected from among methylglycine
diacetate
(MGDA) and its alkali metal salts, glutamic acid diacetate (GLDA) and its
alkali metal
salts, iminodisuccinate, hydroxyethylimine diacetate and
ethyleneiminodisuccinate
and the corresponding alkali metal salts,
(B) at least one organic compound selected from among organic phosphates,
organic
phosphonates and organic phosphites and salts of the abovementioned organic
compounds, and
(C) optionally water,
for application to plants or the ground.
Furthermore, the present invention relates to formulations comprising
(A) one or more aminocarboxylates, selected from among methylglycine diacetate
(MGDA) and its alkali metal salts, glutamic acid diacetate (GLDA) and its
alkali metal
salts, iminodisuccinate, hydroxyethylimine diacetate and
ethyleneiminodisuccinate
and the corresponding alkali metal salts,
(B) at least one organic compound selected from among organic phosphates,
organic
phosphonates and organic phosphites and salts of the abovementioned organic
compounds, and
(C) optionally water.
Furthermore, the present invention relates to a process for the preparation of
the
formulations according to the invention.
It has long been desired to improve the yields of soils as regards fertility.
In this context, it is
not only the fertilization of the soil which plays a role, but also the
control of undesired
plants and animals capable of reducing a crop yield.
CA 2857095 2019-01-04
2
A variety of organic phosphorus-comprising compounds, for example organic
phosphates,
organic phosphonates and organic phosphites and salts of the abovementioned
organic
compounds, have a range of effects on organisms such as weeds, vermin and
undesired
fungi. A problem when applying many of these organic compounds is that they
are capable
of reacting with soil components such as iron oxides, aluminum oxides, layer
silicates,
calcium compounds and magnesium compounds and/or are capable of being adsorbed
by
the former, whereby they are converted into a form which is insoluble in water
and hence no
longer available to plants. This process is also referred to as
mineralization. Depending on
the soil composition, mineralization takes place within a period of 2 to 14
days. Therefore,
the activity is unsatisfactory despite the fact that the quantity available of
organic
phosphorus compounds is high or indeed too high. At the same time, the amount
of active
substances stored in the soil and the environment is constantly being
increased according
to current practice, which is likewise undesired.
A similar problem is that a mineralization of organic phosphorus-comprising
compounds
may also be caused by the alkaline-earth metal ions which may be present in
the water
used for making dilute spray mixture. Depending on the water hardness and the
degree of
dilution, significant amounts of active substance may be eliminated in this
manner.
In many cases, therefore, glyphosate is applied to the soil together with
considerable
amounts of ammonium sulfate. In this context, the amounts of ammonium sulfate
may be
considerable. Thus, EP 0 290 416 discloses a typical concentrate 74 g/I
glyphosate (free
acid), 49 g/I glyphosate nnonoisopropylammonium salt, 120 g/I fatty amine
ethoxylate and
280 g/I ammonium sulfate. Between 100 and 600 liters of formulation are
typically employed
per ha of field. This corresponds to an active substance discharge of 1-6
kg/ha field. The
formulation comprises more ammonium sulfate than active substance.
It was therefore an object to provide formulations whose organic phosphorus
compounds
can be taken up readily by the soil or plants, for example in such a manner
that an
absorption capacity over a period of up to 8 weeks is ensured. It was
therefore an object to
provide uses of formulations by means of which organic phosphorus compounds
can be
taken up readily by soils and in particular plants. It is furthermore an
object to provide a
method by means of which the organic phosphorus compounds can be made readily
bioavailable.
Accordingly, there have been found the uses and formulations defined at the
outset.
CA 2857095 2019-01-04
2a
According to the invention, there is used as least one formulation comprising
(A) one or more aminocarboxylates, also termed aminocarboxylate (A) for short
or else,
summarily, compound (A), selected from among methylglycine diacetate (MGDA)
and its alkali metal salts, glutamic acid diacetate (GLDA) and its alkali
metal salts,
iminodisuccinate, hydroxyethylimine diacetate and ethyleneiminodisuccinate and
the
corresponding alkali metal salts
(B) at least one organic compound, also termed compound (B), selected from
among
organic phosphates, organic phosphonates and organic phosphites and salts of
the
abovennentioned organic compounds, and
(C) optionally water,
for application to plants or the ground.
The invention therefore provides a use of a formulation comprising
(A) one or more aminocarboxylates selected from the group consisting of
methylglycine diacetate (MGDA) and its alkali metal salts, and glutamic acid
diacetate (GLDA) and its alkali metal salts,
(B) at least one organic compound selected from the group consisting of
organic
phosphates, organic phosphonates, organic phosphites and salts thereof, and
(C) optionally water,
for application to plants or the ground.
The invention also provides a formulation comprising
(A) one or more aminocarboxylates selected from the group consisting of
methylglycine diacetate (MGDA) and its alkali metal salts, and glutamic acid
diacetate (GLDA) and its alkali metal salts,
(B) at least one organic compound selected from the group consisting of
herbicides
which are selected from the group consisting of organic phosphates, organic
phosphonates, organic phosphites and salts thereof, and
(C) optionally water.
The invention also provides a method of growing plants, wherein the ground or
plant is
treated at least once with the formulation as defined herein before the plant
in question is
harvested.
The invention also provides a method of storing or transporting at least one
organic
compound (B) selected from the group consisting of herbicides which are
selected from the
CA 2857095 2019-01-04
2b
group consisting of organic phosphates, organic phosphonates, organic
phosphites and
salts thereof, wherein the at least one organic compound (B) is stored and/or
transported in
the form of the formulation as defined herein.
Compound (A) may be present as the free acid or preferably in partially or
fully neutralized
form, in other words as a salt. Counterions which may be selected are, for
example,
inorganic cations, for example ammonium or alkali, preferably Na, K+, or
organic cations,
preferably ammonium which is substituted by one or more organic residues, in
particular
mono-C1-C4-alkylammonium, for example isopropylammonium, furthermore
triethanolammonium, N,N-diethanolammonium, N-mono-Ci-C4-
alkyldiethanolammonium, for
example N-methyldiethanolammonium or _________________________________
CA 2857095 2019-01-04
PF 73107 CA 02857095 2014-05-27
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N-n-butyldiethanolammonium, and N,N-di-Ci-C4-alkylethanolammonium. Alkali
metal ions are
preferred, Na + and K+ especially preferred.
For the purposes of the present invention, aminocarboxylates (A) are
understood as meaning
those organic compounds which include a tertiary amino group which includes
one or two CH2-
000H which group(s) can be partially or fully neutralized, as mentioned above.
In another embodiment of the present invention, aminocarboxylates (A) are
selected from
among those organic compounds which include a secondary amino group which
includes one
or two CH(COOH)CH2-000H which group(s) can be partially or fully neutralized,
as mentioned
above.
In one embodiment of the present invention, aminocarboxylates (A) are selected
from among
iminodisuccinate (IDS) and hydroxyethylinninedisuccinate (HEIDS) and also the
corresponding
alkali metal salts. In another embodiment of the present invention,
aminocarboxylates (A) are
selected among hydroxyethyliminediacetate (HEIDA) and also the corresponding
alkali metal
salts.
Preferred aminocarboxylates (A) and polyaminocarboxylates (A) are those
organic compounds
whose structure is based on an amino acid whose amino group(s) include(s) one
or two CH2-
000H groups and which are tertiary amino groups. In this context, amino acids
may be
selected among L-amino acids, R-amino acids and enantiomer mixtures of amino
acids, for
example the racemates.
In one embodiment of the present invention, compound (A) is selected among
methylglycine
diacetate (MGDA) and glutamic diacetate (GLDA) and their derivates and
preferably their salts,
in particular their sodium and potassium salts. Very especially preferred are
methylglycine
diacetate and the trisodium salt of MGDA.
Compound (B) is selected from among organic phosphates, organic phosphonates
and organic
phosphites and salts of the abovementioned organic compounds. Preferred
compounds (B) are
organic phosphonates.
For the purposes of the present invention, organic phosphates are defined as
compounds which
correspond to the general formula (I)
0
_p_xl
0 \ (I)
X2
In this formula, the variables are defined as follows:
R, is selected from among C1-C20-alkyl, 03-C10-cycloalkyl or C6-C14-aryl,
unsubstituted or at
least monosubstituted by C1-C6-alkyl, phenyl, OH, OR2, NH2, NHR2, N(R2)2, SH,
SR2,
PF 73107 CA 02857095 2014-05-27
' 4
CH2OH, CH2OR2, CH2NH2, CH2NHR2, CH2N(R2)2, CH2SH, CH2SR2, CH2C6hl5,
CH2-COOH, CH2COOM1, (CH2)2-COOH, (CH2)2C00M1, CH2-NH2(+)-CH2COOH,
CH2-NH2(+)-CH2C00 M1, (CH2)2-NH2(+)-CH2000H, (CH2)2-NH2(+)-CH2C00 M1,
CH2-NH-CH2000H, CH2-NH-CH2C00 M1, (CH2)2-NH-CH2COOH,
(CH2)2-NH-CH2C00 Ml;
it being possible for at least one C atom in Ci-C20-alkyl or C3-Cio-cycloalkyl
to be replaced
by oxygen, NH, NR2 or sulfur,
R2 is C1-06-alkyl, phenyl, benzyl, CH2OH, CH2OR2, CH2NH2, CH2NHR2, CH2N(R2)2,
CH2SH,
CH2SR2,
X1 is selected from among OH and 0M1, where M1 is selected from
among alkali metal
cations, for example Nat, Kl-, furthermore alkaline-earth metal cations, for
example Mg2+,
and ammonium ions, unsubstituted or mono- or polysubstituted by C1-C4-alkyl or
CH2CH2OH. Examples of substituted ammonium ions are CH3NH3+, (CH3)2NH2+,
(CH3)3NH+, (CH3)4N+, CH3CH2NH3+, (C21-15)2NH2+, (C2H5)3N1-1+, (C2Hs)4N+,
(CH3)2CHNH3+,
(CH3)2CHNH(CH3)2+, (CH3)2CHNH2(CH3)*, CH3NH(CH2CH2OH)2+, (CH3)2NH(CH2CH2OH)ii,
X2 is selected from among OH, 0M1 and OR1, where two R1 or M1 may be identical
or
different.
For the purposes of the present invention, organic phosphites are defined as
compounds which
correspond to general formula (II)
R1
I 1
0, ,,X
P (II)
X2 .
In this context, the variables are as defined hereinabove.
Compound (B) is preferably selected from organic phosphonates. For the
purposes of the
present invention, organic phosphonates are defined as compounds which
correspond to the
general formula (III)
0
I I
ii 1
R-P-X (III)
\X2
In this context, the variables are as defined hereinabove.
PF 73107 CA 02857095 2014-05-27
In one embodiment of the present invention, compound (B) is selected from
among herbicides,
in particular those with activity against monocotyledonous or dicotyledonous
weeds. Especially
preferred are herbicides with activity against monocotyledonous and
dicotyledonous weeds.
5 In one embodiment of the present invention, compound (B) is selected from
among glyphosate
and salts of glyphosate, for example salts with cations M1. Especially
preferred cations are K*,
the ammonium and the isopropylammonium ion. In this context, glyphosate may be
present in
partially or fully neutralized form.
In one embodiment of the present invention, compound (B) is selected from
among
monoisopropylammonium glyphosate.
In accordance with the invention, one uses formulations which may comprise
water (C).
Formulations according to the invention may comprise water (C). Water may be
present for
example in amounts of from 0.1 to 10% by weight, based on the total
formulation according to
the invention, or the total formulation used in accordance with the invention.
In another
embodiment, a formulation according to the invention, or a formulation used in
accordance with
the invention, comprises more than 10, but up to 95%, of water. In another
embodiment of the
present invention, a formulation according to the invention, or formulation
used in accordance
with the invention, comprises water (C) in the range of from 95.01 to 99.9% by
weight.
Formulations according to the invention may be present as a powder, as moist
powder, a
suspension, as powder slurry or a solution. Formulations according to the
invention may, for
example, be concentrates or spray solutions.
To employ formulations according to the invention, they can be applied to
plants or to the
ground or to growth substrates, for example as an active substance formulation
or in
combination with a fertilizer. To that end, the formulation according to the
invention can be
applied manually or mechanically to soil or growth substrate which is bare or
sustains
vegetation, or formulation according to the invention can be applied manually
or mechanically to
plants.
Examples of suitable plants are vegetables, grasses, cereals, trees, root
crops, bushes, shrubs
and flowers. Especially preferred are oilseed rape, wheat, millet/sorghum,
rye, barley, avocado,
citrus fruit, mango, coffee, deciduous tree crops, grapes and other soft fruit
plants, beans, in
particular soybeans, furthermore maize, tomatoes, cucumbers, in particular
zucchini and salad
cucumbers, pumpkins, furthermore lettuce, potatoes, fodder beet, sugar beet,
paprika,
sugarcane, hops, tobacco, pineapple, palms, in particular coconut palms,
furthermore rubber
trees including Brazilian rubber trees (Hevea brasiliensis), and ornamental
plants, in particular
roses, dahlias, tulips, narcissus, daffodils, carnations and chrysanthemums.
PF 73107 CA 02857095 2014-05-27
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For application purposes, the formulation according to the invention can be
applied over an area
to be treated, for example by aircraft or vehicle, or it can be applied with
the aid of an irrigation
system. Other types of application are spraying and root dosage, liquid or
solid.
In one embodiment of the present use, at least one formulation is used in
accordance with the
invention, which formulation comprises at least one organic compound (D)
selected from among
urea and citric acid and its alkali metal salts. Preferred alkali metal salts
of citric acid are
tripotassium citrate ("potassium citrate") and the trisodium salt of citric
acid ("sodium citrate").
In one embodiment, one will use, according to the invention, at least one
formulation which
comprises at least one inorganic compound (E). Preferred inorganic compounds
(E) are
ammonium salts of mineral acids, in particular ammonium sulfate.
In one embodiment of the present invention, one will use, in accordance with
the invention, at
least one formulation which comprises at least one additive (F) selected from
among wetters,
surfactants, spray adjuvants and spreaders. Especially suitable additives (F)
are surfactants, for
example C8-C20-alkyl sulfates, C8-C20-alkylsulfonates and C8-C20-alkyl ether
sulfates having one
to 6 ethylene oxide units per molecule. Further suitable surfactants are
nonionic surfactants
such as, for example, alkylpolyglucosides and C6-C20-alkylaminoalkoxylates
having, for
example, 2 to 30 alkoxylate units per mole, preferably C6-C20-
alkylaminoethoxylates having for
example 2 to 30 ethylene oxide units per mole, and in particular tallow fatty
amine ethoxylates
having 10 to 20 ethylene oxide units per mole.
In one embodiment of the present invention, at least one formulation
comprising at least one
polyaminocarboxylate is used in accordance with the invention.
For the purposes of the present invention, polyaminocarboxylates (A) are
understood as
meaning those organic compounds which include at least two tertiary amino
groups which,
independently of one another, include in each case one or two CH2-COOH which
group(s) can
be partially or fully neutralized, preferably using alkali metal, more
preferably using Na + or K.
In another embodiment of the present invention, polyaminocarboxylates (A) are
selected from
among those organic compounds which include at least two secondary amino
groups, each of
which includes one CH(COOH)CH2-COOH which group(s) can be partially or fully
neutralized,
as mentioned above.
Preferred polyaminocarboxylates (A) are selected among 1,2-
diaminoethanetetraacetic acid
(EDTA), ethylenediaminedisuccinate (EDDS), tetraacetylmethylenediamine,
tetraacetylhexylenediamine, diethylenetriaminepentaacetate (DTPA),
hydroxyethylenediaminetriacetate (HEDTA) and their respective salts, in
particular alkali metal
salts, very especially preferably the sodium salts and potassium salts, and
mixed sodium
potassium salts.
PF 73107 CA 02857095 2014-05-27
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The present invention furthermore relates to formulations comprising
(A) one or more aminocarboxylates, selected from among methylglycine diacetate
(MGDA)
and its alkali metal salts, glutamic acid diacetate (GLDA) and its alkali
metal salts,
iminodisuccinate, hydroxyethylimine diacetate and ethyleneiminodisuccinate and
the
corresponding alkali metal salts,
(B) at least one compound (B) selected from among herbicides which are
selected from
among organic phosphates, organic phosphonates and organic phosphites and
salts of
the abovementioned organic compounds, and
(C) optionally water.
Aminocarboxylates (A), polyaminocarboxylates and compounds (B) are described
hereinabove.
In one embodiment of the present invention, formulation according to the
invention comprises at
least one aminocarboxylate (A) and at least one polyaminocarboxylate.
In one embodiment of the present invention, compound (B) is selected from
among herbicides
with activity against monocotyledonous or dicotyledonous weeds. Especially
preferred are
herbicides with activity against monocotyledonous and dicotyledonous weeds.
Compound (B) is selected from among organic phosphates, organic phosphonates
and organic
phosphites and salts of the abovementioned organic compounds.
It is especially preferred to select compound (B) from among glyphosate and
salts of
glyphosate, in particular monoisopropylammonium glyphosate.
In one embodiment of the present invention, formulation according to the
invention comprises:
in total in the range of from Ito 90% by weight, preferably 10 to 50% by
weight, of
aminocarboxylate (A) and polyaminocarboxylate (A), where either the content of
aminocarboxylate (A) or the content of polyaminocarboxylate (A) may be zero,
and
in total in the range of from 0.1 to 25% by weight, preferably 0.25 to 5% by
weight, of compound
(B).
In the context, % by weight refer in each case to the solids content of
formulation according to
the invention.
Formulation according to the invention may furthermore comprise water (C)
In one embodiment of the present invention, formulation according to the
invention comprises at
least one further substance selected from among
(D) organic compounds which are selected from among urea and citric acid and
its alkali
metal salts,
(E) inorganic substances, preferably ammonium salts of mineral acids, in
particular
ammonium sulfate,
PF 73107 CA 02857095 2014-05-27
8
(F) additives, selected from among wetters, surfactants, spreaders and spray
adjuvants.
Organic compounds (D), inorganic substances (E), polyaminocarboxylates and
additives (F) are
described hereinabove.
Especially suitable additives (F) are surfactants, for example C8-C20-alkyl
sulfates, C8-C20-
alkylsulfonates and Cs-C20-alkyl ether sulfates having one to 6 ethylene oxide
units per
molecule. Further suitable surfactants are nonionic surfactants such as, for
example,
alkylpolyglucosides and Co-C20-alkylaminoalkoxylates, preferably Cs-C20-
alkylaminoethoxylates,
and in particular tallow fatty amine ethoxylates.
In one embodiment of the present invention, formulation according to the
invention comprises
in total in the range of from zero to 25% by weight, preferably 1 to 10% by
weight, of organic
compound(s) (D),
in total in the range of from zero to 5% by weight, preferably 0.1 to 2.5% by
weight, of inorganic
substance(s) (E),
in total in the range of from zero to 25% by weight, preferably 1 to 15% by
weight, of additive(s)
(F),
in the range of from zero to 10% by weight of polyaminocarboxylate.
In this context, % by weight refer in each case to the solids content of
formulation according to
the invention.
In one embodiment of the present invention, formulation according to the
invention has a pH in
the range of from 4 to 11, preferably from 5 to 9. In a specific variant,
formulation according to
the invention has a pH in the range of from 9 to 11.
Formulations according to the invention can be used particularly
advantageously for efficiently
improving the herbicidal activity of organic compounds (B) on useful plants
without applying
large amounts of undesirable compounds or without large amounts of undesirable
compounds
reaching the ground water, and which would lead to a general pollution or
inland watercourses
and/or without accumulation via the food chain. Especially advantageous is the
use of
formulations according to the invention in environments with frequent
precipitation, in which
organic compounds (B), even when applied analogously to foliar fertilization,
are washed into
the ground to a considerable extent, but, when using formulation according to
the invention, no
longer become ineffective in the soil as the result of mineralization.
A further subject matter of the present invention is a process for the
preparation of formulations
according to the invention, also referred to as preparation process according
to the invention
within the scope of the present invention.
In one embodiment of the preparation process according to the invention, a
procedure is
followed in which:
PF 73107 CA 02857095 2014-05-27
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(A) one or more aminocarboxylate(s) (A), selected from among methylglycine
diacetate
(MGDA) and its alkali metal salts, glutamic acid diacetate (GLDA) and its
alkali metal
salts, iminodisuccinate, hydroxyethylimine diacetate and
ethyleneiminodisuccinate and
the corresponding alkali metal salts, and
(B) at least one organic compound selected from among herbicides which are
selected from
organic phosphates, organic phosphites and organic phosphonates and salts of
the
abovementioned compounds,
are mixed with each other in the presence of water (C) and
optionally all or some of the water (C) is removed.
In one embodiment of the present invention, at least one compound (A) and at
least one
compound (B) are dissolved in water (C), for example in 10% by volume up to
the 10-fold
amount (based on volume), based on the total of compound (A) and inorganic
compound (B).
Thereafter, all or some of the water (C) may be removed.
In another embodiment of the present invention, at least one compound (B) is
suspended in a
solution of at least one compound (A) in water (C), for example in 10% by
volume up to the 10-
fold amount (based on volume), based on the total of compound (A) and compound
(B).
Thereafter, all or some of the water (C) may be removed.
In another embodiment of the preparation process according to the invention, a
procedure is
followed in which, in the presence of water (C) and
(A) one or more aminocarboxylate(s) (A), selected from among methylglycine
diacetate
(MGDA) and its alkali metal salts, glutamic acid diacetate (GLDA) and its
alkali metal
salts, iminodisuccinate, hydroxyethylimine diacetate and
ethyleneiminodisuccinate and
the corresponding alkali metal salts or
(B) at least one compound, preferably at least two compounds (B), in each case
selected
from among herbicides which are selected from among organic phosphates,
organic
phosphites and organic phosphonates and salts of the abovementioned compounds,
is prepared in the presence of at least one inorganic substance (E) and
optionally all or some of the water (C) is removed.
It is therefore possible for example to use potassium hydroxide as the
inorganic substance (E)
and thereby to prepare the potassium salt of compound (B) in situ.
It is preferred to select one or more ammonium salts of mineral acids as the
inorganic
substance (E), in particular ammonium sulfate.
In another variant, potassium hydroxide is employed as inorganic substance (E)
and is mixed in
the presence of water (C) with aminocarboxylate(s) (A) or
polyaminocarboxylate(s) as the free
acid(s), whereby potassium salts of aminocarboxylate(s) (A) or
polyaminocarboxylate(s) are
prepared.
PF 73107 CA 02857095 2014-05-27
Optionally, and in each case before or after removal of the water (C), a
mixture may be made in
addition with at least one further substance selected from among
(D) organic compounds which are selected from among urea and citric acid and
its alkali metal
salts,
5 (E) inorganic substances, in particular ammonium sulfate, and
(F) additives selected from among wetters, surfactants, spreaders and spray
adjuvants or with
at least one polyaminocarboxylate.
In another embodiment, a mixture may be made in addition with at least one
further substance
10 .. selected from among
(D) organic compounds which are selected from among urea and citric acid and
its alkali metal
salts,
(E) inorganic substances, in particular ammonium sulfate, and
(F) additives selected from among wetters, surfactants, spreaders and spray
adjuvants, or with
at least one polyaminocarboxylate without removing the water (C).
In one embodiment of the preparation process according to the invention, a
procedure is
followed in which all or, preferably, some of the water (C) is removed, for
example by
evaporation, distillation, freeze-drying, in particular by spray-drying or
spray granulation. In
another embodiment, the water employed during the preparation according to the
invention
remains in the formulation according to the invention.
A further subject matter of the present invention is a method of fertilizing
plants, wherein at least
one formulation according to the invention is applied mechanically or manually
to ground and/or
plants.
Formulations according to the invention can be stored and transported
particularly readily.
Therefore, a further subject matter of the present invention is a method of
storing compounds
(13), wherein the compounds (B) are stored in the form of the formulation
according to the
invention. Therefore, a further subject matter of the present invention is a
method of
transporting compounds (B), wherein the compounds (B) are stored in the form
of the
formulation according to the invention.
In the context of the present invention, storing is understood as meaning that
compounds (B)
are retained over a period of at least one day without performing a chemical
reaction on
compound (B).
In the context of the present invention, transporting is understood as meaning
that compound
(B) is conveyed over a certain distance with the aid of a conveyance means
outside a chemical
production plant, for example at least 100 m, preferably 1 km to 10 000 km.
Suitable
conveyance means are railway cars, trucks, ships and aeroplanes.
PF 73107 CA 02857095 2014-05-27
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Storage in accordance with the invention may be performed in storage
containers of any size,
for example in silos, bins, cellars and tanks made of plastic (IBC) or of
metal. The fill level of the
container is from 1-100% by volume and the dilution may be chosen as desired
up to 10 000/1.
In accordance with the invention storage may be effected for example for at
least one day, with
at least two days up to one year being preferred.
Transporting in accordance with the invention may be effected over a period of
from 1 to 10
days.
For example, storage or transporting according to the invention may be
effected at a
temperature in the range from zero to 60 C, but the temperature may also
exceed or be below
this value. For example, storage or transporting in accordance with the
invention may also be
effected under freezing conditions, for example at -70 to -0.5 C.
The invention is illustrated by working examples.
All % are % by weight unless expressly stated otherwise.
Examples:
I. Preparation of concentrates
1.1 Preparation of comparative concentrate V-K.1
275 g of ammonium sulfate (E.1) were dissolved in 400 g of water. Thereafter,
70 g of
glyphosate (free acid) (B.1) and 56 g of glyphosate monoisopropylammonium salt
(B.2) were
added. Thereafter, water was added to a total weight of 1000 g. This gave
comparative
concentrate V-K.1.
1.2 Preparation of formulation K.2 according to the invention
70 g of glyphosate (free acid) (B.1) and 56 g of glyphosate
monoisopropylammonium salt (B.2)
were dissolved in 620 g of a 40% by weight strength aqueous solution of
methylglycinediacetate
trisodium salt (A.1). Thereafter, water was added to a total of 1000 g. This
gave formulation K.2
according to the invention.
1.3 Preparation of formulation K.3 according to the invention
70 g of glyphosate (free acid) (B.1) and 56 g of glyphosate
monoisopropylammonium salt (B.2)
.. were dissolved in 710 g of a 40% by weight strength aqueous solution of
methylglycinediacetate
tripotassium salt (A.2). Thereafter, water was added to a total of 1000 g.
This gave formulation
K.3 according to the invention.
PF 73107 CA 02857095 2014-05-27
12
1.4 Preparation of formulation K.4 according to the invention
70 g of glyphosate (free acid) (6.1) and 56 g of glyphosate
monoisopropylammonium salt (13.2)
were dissolved in 710 g of a 40% by weight strength aqueous solution of
methylglycinediacetate
trisodium salt (A.1). Thereafter, 120 g of ammonium sulfate (E.1) were added.
Thereafter, water
was added to a total of 1000 g. This gave formulation K.4 according to the
invention.
1.5 Preparation of formulation K.5 according to the invention
70 g of glyphosate (free acid) (B.1) and 56 g of glyphosate
monoisopropylammonium salt (B.2)
were dissolved in 670 g of a 40% by weight strength aqueous solution of
glutamic acid diacetate
trisodium salt (A.3). Thereafter, water was added to a total of 1000 g. This
gave formulation K.5
according to the invention.
1.6 Preparation of comparative concentrate V-K.6
275 g of ammonium sulfate (E.1) were dissolved in 400 g of water. Thereafter,
70 g of
glyphosate (free acid) (B.1) and 56 g of glyphosate monoisopropylammonium salt
(B.2) were
added. Thereafter, 120 g of ethoxylated tallow fatty amine (15 ethylene oxide
units per mole)
were added. Thereafter, water was added to a total weight of 1000g. This gave
comparative
concentrate V-K.6.
1.7 Preparation of formulation K.7 according to the invention
70 g of glyphosate (free acid) (B.1) and 56 g of glyphosate
monoisopropylammonium salt (B.2)
were dissolved in 620 g of a 40% by weight strength aqueous solution of
methylglycinediacetate
trisodium salt (Al). Thereafter, 120 g of ethoxylated tallow fatty amine (15
ethylene oxide units
per mole) were added. Thereafter, water was added to a total weight of 1000 g.
This gave
formulation K.7 according to the invention.
1.8 Preparation of formulation K.8 according to the invention
70 g of glyphosate (free acid) (B.1) and 56 g of glyphosate
monoisopropylammonium salt (B.2)
were dissolved in 710 g of a 40% by weight strength aqueous solution of
methylglycinediac,etate
tripotassium salt (A.2). Thereafter, 120 g of ethoxylated tallow fatty amine
(15 ethylene oxide
units per mole) were added. Thereafter, water was added to a total weight of
1000 g. This gave
formulation K.8 according to the invention.
1.9 Preparation of formulation K.9 according to the invention
70 g of glyphosate (free acid) (B.1) and 56 g of glyphosate
monoisopropylammonium salt (13.2)
were dissolved in 730 g of a 40% by weight strength aqueous solution of
glutamic acid diacetate
trisodium salt (A.3). Thereafter, 120 g of ethoxylated tallow fatty amine (15
ethylene oxide units
PF 73107 CA 02857095 2014-05-27
13
per mole) were added. Thereafter, water was added to a total weight of 1000 g.
This gave
formulation K.9 according to the invention.
1.10 Preparation of formulation K.10 according to the invention
20 g of glyphosate (free acid) (B.1) and 14 g of glyphosate
monoisopropylammonium salt (8.2)
were dissolved in 510 g of a 40% by weight strength aqueous solution of
methylglycinediacetate
tripotassium salt (A.2). Thereafter, 90 g of ethoxylated tallow fatty amine
(15 ethylene oxide
units per mole) were added. Thereafter, water was added to a total weight of
1000 g. This gave
formulation K.10 according to the invention.
1.11 Preparation of spray solutions (general protocols)
1.11.1 Preparation of spray solutions I
50 g of a formulation K.2 according to the invention were diluted with water
(water hardness
110 ppm) to 1000 g (1/20). This gave spray solution SL.2 according to the
invention.
An analogous procedure was followed with comparative concentrate V-K.1 and
with the
formulations K.3 to K.5 according to the invention. This gave comparative
spray solution V-SL.1
and the spray solutions SL.3 to SL.5 according to the invention, respectively.
1.11.2 Preparation of spray solutions 11
1 g of a formulation K.7 according to the invention were diluted with water
(water hardness
110 ppm) to 1000 g (1/1000). This gave spray solution SL.7 according to the
invention.
An analogous procedure was followed with comparative concentrate V-K.6 and
with the
formulations K.5 to K.10 according to the invention. This gave comparative
spray solution V-
SL.6 and the spray solutions SL.8 to SL.10 according to the invention,
respectively.
II. Studies on soil segments
11.1 Mineralization experiments, general protocol following the example SL.2
1 kg of loose sediment of ground earth from South Germany with a water content
of 23%, a pH
of 6.1-6.3 and a mineral fraction of 45% (composition of the mineral fraction:
33% quartz, 20%
carbonates, 20% mica, 9% clay mineral, 7% feldspar, 3% iron oxide; with an Al
content of 1.7%,
a Ca content of 1.4%, an Fe content of 2.1%, a phosphate content (determined
as P205) of
240 mg P205/kg soil) were placed in a round vessel (diameter 12 cm).
The soil was sprayed with 240 ml of spray solution SL.2 according to the
invention, using a
diffuser, diffusing, over a period of 48 hours, in each case 30 ml of the
spray solution SL.2
according to the invention over the surface of the brown earth every 6 hours.
Thereafter, the soil
was stored for a further 72 h at 20 C without covering the vessels.
,
PF 73107 CA 02857095 2014-05-27
s
' 14
For the analysis, the soil was subsequently transferred into a 2-liter vessel
and made into a
slurry with 1 liter of water at 20 C. The mixture was stirred for 20 minutes
and the soils were
separated from the filtrate using a suction filter. Slurrying and filtration
were repeated twice. The
water of the collected filtrates were stripped off in a rotary evaporator. The
residue was
analyzed for the glyphosate content (HPLC).
Thus the dosage of glyphosate, based on the acid, amounted to 1340 mg. The
amount of eluted
glyphosate and the amount of mineralized glyphosate fixed in the soil were
calculated
accordingly.
An analogous procedure was followed for studying the comparative spray
solution V-SL.1 and
the comparative spray solutions SL.3 to SL.5. The results are compiled in
Table 1.
Table 1: Studies of soil samples
V-SL.1 SL.2 SL.3 SL.4
SL.5
Mineralized 1236 410 250 246 700
glyphosate
[mg]
Mineralized 92.2 30.6 18.7 18.4
52.2
glyphosate
[0/0]
Eluted 104 930 1090 1094 640
glyphosate
[mg]
11.2 Long-term mineralization experiments as a function of the sample depths,
protocol following
the example SL.7
In a further experiment, agricultural soil (loose-sediment brown earth) in
roof-covered plots in
each case 1 m2 in size were treated with spray solutions II over a period of
60 days. The depth
of the loose-sediment brown earth strata was 90 cm.
A plot was treated with in each case a total of 10 liters of SL.7/m2 over a
period of 8 weeks and
artificially irrigated with 50 liters of water/m2 (water hardness < 10 ppm).
To this end, the plot
was sprayed every 3 days with 0.5 liters of SL.7 followed by irrigation for 6
hours with 2.5 I
water (water hardness < 10 ppm). After the treatment, which lasted for 8
weeks, irrigation was
continued for a further 8 weeks without applying other substances (3
liters/m2every 3 days).
Thereafter, cores down to a depth of 80 cm were sampled using an auger
(diameter 10 cm). 4
cores were removed to obtain representative means for the subsequent studies.
The cores
were divided into disks with a thickness of 10 cm. The amount of the
glyphosate fraction which
PF 73107 CA 02857095 2014-05-27
could be eluted with water was determined for these disks, using in each case
a procedure as
described in Ill.
Table 2: Studies of soil samples in long-term experiments
5
V-SL.6 SL.7 SL.8 SL.9 SL.10
[mg) eluted 82 360 393 387 93
glyphosate
depth 0-10 cm
[mg] eluted 22 290 301 279 26
glyphosate
depth 10-20 cm
[mg) eluted 9 47 49 39 7
glyphosate
depth 20-30 cm
[mg] eluted 15 15 12
glyphosate
depth 40-50 cm
[mg] eluted 4 3
glyphosate
depth 60-70 cm
[mg] eluted
glyphosate
depth 70-80 cm
The experimental findings demonstrate that the availability of glyphosate by
the addition of
aminocarboxylates (A) is at a high level despite a certain water hardness
(spray solution) and .
despite the presence of soil minerals. Even SL.10, which comprises only 26% of
the glyphosate
10 fraction, compared with V-SL.6, outperformed V-SL.6, in respect of the
elutable glyphosate
fraction.
