CA1293974C - Preparation of alkanolamine salts of carboxylic acid herbicides - Google Patents
Preparation of alkanolamine salts of carboxylic acid herbicidesInfo
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- CA1293974C CA1293974C CA000526348A CA526348A CA1293974C CA 1293974 C CA1293974 C CA 1293974C CA 000526348 A CA000526348 A CA 000526348A CA 526348 A CA526348 A CA 526348A CA 1293974 C CA1293974 C CA 1293974C
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- mixture
- diethanolamine
- alkanolamine
- herbicide
- weight
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Abstract
ABSTRACT
The present invention is directed to a method of preparing a substantially water-free alkanolamine salt of any of the herbicides, 2,4-D, MCPA, MCPP, triclopyr, clopyralid, picloram, benazolin, dicamba, or a mixture of any two or more of such herbicidal compounds which comprises (a) warming gradually while stirring in the absence of an added aqueous or organic solvent medium a substantially equimolar mixture of one or more of said herbicides and an alkanolamine; and continuing to warm and stir the mixture until a paste or incipient melt is formed;
(b) allowing the mixture to cool; and (c) continuing to stir the mixture as it cools until a free-flowing powder is obtained.
The present invention is directed to a method of preparing a substantially water-free alkanolamine salt of any of the herbicides, 2,4-D, MCPA, MCPP, triclopyr, clopyralid, picloram, benazolin, dicamba, or a mixture of any two or more of such herbicidal compounds which comprises (a) warming gradually while stirring in the absence of an added aqueous or organic solvent medium a substantially equimolar mixture of one or more of said herbicides and an alkanolamine; and continuing to warm and stir the mixture until a paste or incipient melt is formed;
(b) allowing the mixture to cool; and (c) continuing to stir the mixture as it cools until a free-flowing powder is obtained.
Description
37~
~ lerbicides such as 2,4-D, MCPA, MCPP, triclopyr, clopyralid, picloram, benazolin, dicamba or mixtures of any two or more of such herbicides are known~ Processes for making these herbicides utilize aqueous or organic solvents which must be separated from the reaction mixture in order to formulate the desired herbicide product~ Separation of the solvents from the reaction mixture after formation of the desired product requires multiple steps and high energy requirements. It would be desir-able to employ a process for preparing these herbicides which eliminates using added solvents. It is also desirable to be able to prepare the alkanolamine salts of these herbicides and ship them in the dxy water-free condition to save on weight.
The present invention is directed to a method of pre-paring a substantially water-free alkanolamine salt of herbicides, preferably 2,4-D, MCPA, MCPP, triclopyr, clopyralid, picloram, benazolin, dicamba, or a mixture of any two or more of such herbi-cidal compounds which comprises (a) warming gradually while stirring in the absence of an added aqueous or organ:ic solvent medium a sub-stantially equimolar mixture of one or more of said herbicides and an alkanolamine; and continuing to warm and stir the mixture until a paste or incipient melt is formed;
(b) allowing the mixture to cool; and (c) continuing to stir the mixture as it cools until a free-flowing powder is obtained.
C
-~3979~
~ lerbicides such as 2,4-D, MCPA, MCPP, triclopyr, clopyralid, picloram, benazolin, dicamba or mixtures of any two or more of such herbicides are known~ Processes for making these herbicides utilize aqueous or organic solvents which must be separated from the reaction mixture in order to formulate the desired herbicide product~ Separation of the solvents from the reaction mixture after formation of the desired product requires multiple steps and high energy requirements. It would be desir-able to employ a process for preparing these herbicides which eliminates using added solvents. It is also desirable to be able to prepare the alkanolamine salts of these herbicides and ship them in the dxy water-free condition to save on weight.
The present invention is directed to a method of pre-paring a substantially water-free alkanolamine salt of herbicides, preferably 2,4-D, MCPA, MCPP, triclopyr, clopyralid, picloram, benazolin, dicamba, or a mixture of any two or more of such herbi-cidal compounds which comprises (a) warming gradually while stirring in the absence of an added aqueous or organ:ic solvent medium a sub-stantially equimolar mixture of one or more of said herbicides and an alkanolamine; and continuing to warm and stir the mixture until a paste or incipient melt is formed;
(b) allowing the mixture to cool; and (c) continuing to stir the mixture as it cools until a free-flowing powder is obtained.
C
-~3979~
After preparation of the cooled powder from step (c), the cooled powder may be optionally treated by (d) dry blending the cooled powder with from about 0.2 to about 2 percent by weight of an agriculturally accep-table sequestrant; from about 0.5 to about 2 percent by weight of an agriculturally acceptable surfactant and from about 0.5 to about 2 percent by weight of an anticaking agent.
According to another aspect of the present invention there is provided the method of preparing substantially water-free water-dispersible herbicidal product of a phenyl-, phenoxy- or oxobenzothiazolyl 2-propanoic acid or acetic acid herbicide which comprises:
(a) warming gradually while stirring, in the absence of a solvent medium, a substantially stoichiometric mixture of one or more of said herbicides and diethanolamine, said mixture having added thereto from about 7 to about 15 percent by weight oE
ethanolamine based on the weight of diethanolamine employed; and (b) continuing to warm and stir the mixture until a paste or incipient melt is formed;
(c) allowing the mixture to cool;
(d) continuing to stir the mixture as it cools until a free-flowing powder is obtained; and (e) dry blending the cooled powder with from about 0.2 to 2 percent by weight of an agriculturally acceptable sequestrant, from about 0.5 to about 2 percent by weight of an agriculturally g~
- 2a - 73776-11 accep-table surfactant and from about 0.5 to about 2 percent by weight of an anticaking agent.
The herbicide "2,4-D" refers to the compound known as (2~4-dichlorophenoxy~ acetic acid, a white crystalline solid, having a melting point o~ 135 to 138 Centigrade (C) (technical) and 140 to 141 (pure).
The herbicide "MCPA" refers to the compound known as metaxon or [(4-chloro-O-tolyl)oxy]acetic acid ~ ~ 3 which is a light brown solid having a melting point of 118~ to 119C (pure) or 99 to 107C (technical).
The herbicide "MCPP" refers to the compound known as mecoprop or [2-(2-methyl-4-chlorophenoxy)--propionic acid], which is a colorless crystalline solid having a melting point of 94 to 95C.
The herbicide "triclopyr" refers to the compound [(3,5,6-trichloro-2-pyridinyl)oxy]acetic acid having a melting point of 148 to 150C.
The herbicide "clopyralid" refers to the compound 3,6-dichloropicolinic acid or by code name DOWCO 290, of The Dow Chemical Company, Midland, Michigan. Clopyralid is a white, crystalline solid having a melting point of 151 to 152C.
The herbicide "picloram" refers to the compound 4-amino-3,5,6-trichloropicolinic acid, a white powder which decomposes before melting.
The herbicide "benazolin" refers to the compound 4-chloro-2-oxobenzothiazolin-3-ylacetic acid, which has a melting point of 189C.
The herbicide "dicamba" refers to the compound 3,6-dichloro-o-anisic acid, which is a white crystalline solid (reference grade) or a brown crystalline solid (technical acid) having a melting point of 114 to 116C.
The term "alkanolamine" is intended to mean any one or more of ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine or triisopropanolamine, which are capable of forming a 31,494-F -3-~ 7 crystalline salt of any of` sa.id herbicides which is a solid at room temperature.
The term "ethanol amine" (.MEA) refers to the compound known as ~-aminoethanol or 2-hydroxyethylamine having the formula HOCH2CH2NH2o The term "diethanolamine" (DEA) refers to the compound known as di(2-hydroxyethyl)amine having the formula (HOCH2CH2)2NH.
The term "triethanolamine" (TEA) refers to the compound known as tri(2-hydroxyethyl)amine having the formula (HOCH2CH2)3N.
The term "isopropanolamine" (MIPA) refers to the compound known as 2-hydroxypropylamine or 1-amino-2-propanol) having the formula CH3CH(OH)CH2NH2.
The term "diisopropanolamine" (DIPA) refers to the compound having the formula (CH3CHOHCH2)2NH.
The term "triisopropanolamine" refers to the compound having the formula N(C3H60H)3.
The alkanolamines are known compounds and can be prepared by reaction of ethyloxide and ammonium to give a mixture of mono-, di-, and triethanolamines.
Where diethanolamine and ethanolamine are jointly employed7 the proportions of diethanolamine to ethanolamine in the alkanolamine mixture can range from about 7 to about 15 percent by weight of ethanolamine, based on the total weight of diethanolamine, more preferably from about 7 to about 12 percent by weight based on the weight of the diethanolamine employed.
31,494-F -4-~ ~ 3 ~7 A preferred mixture of the alkanolamine is a 50:50 mixture by weight oP diethanolamine and ethanolamine.
In preparing the substantially water-free alkanolamine salt, quantities of the phenyl, phenoxy or oxobenzothiazolyl alkanoic acid herbicide are warmed gradually to a temperature at or below the melting temperature of the herbicide. To the warmed herbicide, a substantially~equimolar amount of an alkanolamine described hereinbefore is added. The mixture of the herbicide and alkanolamine is continuously warmed and stirred until a paste or an incipient melt is formed.
Upon formation of the paste or incipient melt, the mixture is allowed to cool, and the cooling mixture is stirred until a free-flowing powder is obtained. In general, the alkanolamine salts of the invention are freely water soluble. This is clearly preferred.
The alkanolamine salts prepared according to the invention have substantially the same herbicidal properties as the alkanGlamine salts prepared in aqueous or organic solvent reaction medium.
Optionally and preferably, sequestrants, surfactants and anticaking agents can be further admixed with the free-flowing powder to improve the handling and/or herbicidal efficacy properties of said herbicide compounds.
Agriculturally acceptable sequestrants include, but are not limited to, ethylenediamine tetraacetic acid, cLtric acid or a diglycolic acid. The amount of sequestrant added to the free-flowing powder can range 31,494-F -5-3~791 from about 0.2 to about 2 percent by weight of the final herbicide product.
Agriculturally acceptable surfactants or wetting agents include, but are not limited to, sodium9 mono- and dimethyl napthalene sulfonates. A preferred surfactant is Petro-Ag Special U.F., product of Petro Chemicals Corporation9 Fort Worth, Texas. The amount of surfactant added to the free-flowing powder can range from about 0.5 to about 2 percent by weight of the final herbicide product.
Agriculturally acceptable anticaking agents include, but are not limited to, fumed silica or hydrated reprecipitated silica. A preferred anticaking agent is Sipernat 22, trademark of the Degusson Corporation, Teterboro, New Jersey. The amount of anticaking agent addèd to the free-flowing powder can range from about 0.5 to about 2 percent by weight of the final herbicide product.
The sequestrants, surfactants and anticaking agents can be dry blended to the cooled powder to form the desired herbicide product.
The ~ollowing examples illustrate the present invention and the manner by which it can be practiced but, as such, should not be construed as limitations upon the overall scope of the same.
Example l On mixing 256.5 grams (g) (1.0 mole) of triclopyr ancl 105 grams (1.0 mole) of diethanolamine, a damp compressible powder was obtained. This mixture was warmed and stirred simultaneously. The mixture 31,494-F -6-~r~ 3~7~
~radually became paste-like and then, without ~orming a true melt, started to thickenO Heating was stopped but stirring was continuedO As the reaction mixture cooled it turned into a free-flowing powder that was readily soluble in water.
Example_2 A clear melt was made by gradually warming and stirring 44.2 g (0.2 mole) of 2,4-D with 2100 g (0.2 mole) of diethanolamine. On cooling and stirring the melt, the solid herbicide amine salt was obtained in free-flowing powder form.
Example 3 In a sïmilar manner, as in Example 2, a free-flowing powder was formed on reacting 24.1 g (0.10 mole) of picloram and 10.5 g (0.1 mole) of diethanolamine salt.
Example 4 A dry mixture was prepared by grinding 10 g of the 2,4-D amine salt as prepared in Example 2 and 2 g of the picloram amine as prepared in Example 3 together with a mortar and pestle until a uniform blend was obtained. The dry mixture was free-~lowing and readily water soluble. On applying an aqueous solution of the ary mixture to broadleaf weedy plants at a herbicidally effective rate, the expected spectrum of weedy planks is controlled to the extent predicted from known uses of the aeti~e ingredient amine salts separately applied.
31,494-F -7-Example 5 A 44.2 g (0.2 mole) portion of 2,4-D and 21.0 g (0.2 mole) of diethanolamine were reacted and made into a free-flowing powder in the same manner as described in Example 2.
Example 6 In a similar manner, as in Example 2, 43.0 g (0.2 mole) of mecoprop was reacted with 21.0 g (0.2 mole) of diethanolamine, and 22.0 g (0.10 mole) of dicamba was reacted with 10.5 g (0.10 mole) of diethanolamine, in both cases forming a free-flowing powder.
A dry mixture was then made by dry blending 26 g of the 2, 4-D salt, 13 g of t~e mecoprop salt and 2.5 g of the dicamba salt to form a useful, stable readily water soluble herbicidal mixture. On applying an aqueous solution of the three-component dry mixture to broadleaf weedy plants at a herbicidally effective rate the expected spectrum of weedy plants is controlled to the extent predicted from known uses of the active ingredient salts separately applied.
Example 7 Using the same procedures, as in Examples 2 and 5, 25.0 g of 3,6-dichloropicolinic acid were reacted with 13.7 g (0.13 mole) of diethanolamine and 25.0 g (0.10 mole) of benazolin were reacted with 10.8 g of (0.10 mole) of diethanolamine to form free-flowing salt powders. A 15 g portion of each salt powder was thoroughly dry blended together to provide a useful, stable, free-flowing freely water soluble herbicidal 31,494-F -8-~ 3~3 _9_ mixture. On applying an aqueous solution of the two-component mixture alone or with a small amount of surfactant added to broadlea~ weedy plants at a herbicidally effective rate, the expected spectrum of weedy plants is controlled to the extent predicted from known uses o.f the active ingredient salts separately applied.
Example A mixture of 14.0 g (0.06 mole) of picloram and 38.4 g (0.361 mole) of diethanolamine was warmed and stirred together until complete reaction of the picloram was shown by formation of a clear melt. Then 68.0 g (0.31 mole) of 2,4-D was added to the melt, and the melt stirred as it cooled, forming a free-flowing powder. The free-flowing powder was found to be readily water soluble. The herbicidal properties of the picloram and 2,4-D salts are substantially the same as that of the diethanolamine salts made in other ways.
Example 9 A mixture of 32.0 g (0.14 mole) of 2,4-D, 1~.0 g (0.07 mole) of mecoprop, 3.0 g (0.01 mole) of dicamba and 25.0 g (0.23 mole) of diethanolamine was gradually warmed and stirred together sufficiently to obtain a clear melt, then stirred while the melt cooled and turned into a free flowing powder. The co-reacted 3 salts so-prepared are readily water soluble, and the herbicidal properties are substantially not changed by the method of making the salts. The mixture is a useful herbicidal product that is conveniently and economically handled and transported.
31,494-F -9-~ o ~3~3'7~
Example 10 A mixture of 25.0 g (0.13 mole) of 3.6-dichloropicolinic acid (clopyralid) 9 25.0 g of benazolin (0.10 mole) and 24.5 g (0.23 mole) of diethanolamine was gradually warmed and stirred together sufficiently to obtain a clear melt, then stirred while the melt cooled into lumps which readily broke up on continued stirring to form a free-flowing powder. The co-reacted salts so-prepared are readily water soluble and the herbicidal properties are substantially not changed by the method of making the salts. The mixture is a useful herbicidal product that is conveniently and economically handled and transported.
Example 11 The diethanolamine salts of 2,4-D, mecoprop and dicamba are prepared separately by reacting 32.0 g of 2,4-D, 16.0 g of mecoprop and 3.0 g of dicamba with respective stoichiometric amounts of diethanolamine in the manner described in`Example 1, each forming a free-flowing powder. The so-obtained dry powders are thoroughly dry-blended together to form a useful herbicidal product that is readily water soluble.
The melting temperature of the blended powders was determined along with that of the combination 3 products of Examples 2, 7, 8, 9 and 10. Each combination product was passed through a 30 mesh sieve (U.S. Sieve Series) and the underflow used for ease of water solubility tests and pH determination of a 5 percent by weight aqueous solution of each combination product. From the sieved material, in each case, 5 +
31,494-F -lO-Z~3~
0.1 g of powder was measured out and placed in a lO0 milliliter (ml~ graduated cylinder. Deionized water having a temperature of 22C9 and a pH of 6.7 was added to each cylinder to bring the volume to 100 ml and the cylinder stoppered. The cylinder, in each case, was inverted manually each seco~d in a uniform manner.
After every six inversions, the contents of the cylinder were inspected for undissolved solids and the number of inversions required to obtain complete solution of the solids noted. The pH of the resulting solutions was determined with a conventional pH meter equipped with a combination glass electrode.
3o 31,494-F -ll-~2~3~7~
The results of the foregoing tests are summarized in the following Table 1:
_able 1 PHYSICAL PROPERTIES OF COMBINATION SALT PRODUCTS
, . . . n_ _ __ Comblnation Product Tempera- ¦nver- pH of 5%
____ _ _ A. 2,4-D ~ picloram _ _ . _ _ ._ . _ _ -Dry mixed salts 73.5 44 5.2 ~ _ ~ . _ -Co-reacted salts 74.5 50 4.8 _~ _ . ..
B. 2,4 D ~ mecoprop 1 ~ . . , _ ~ .
, -Dry mixed salts57 to 74 26 5.1 . _. . . __ -Co-reacted salts59 to 71 38 4.9 _ ~ _ , C. Clopyralid~benazolin ~_ . . . . .
-Dry mixed salts 118 to 20 7.4 _ -Co-reacted salts 110 to 28 7.4 Example 12 A water jacketed blender was charged with 1875 g of 2,4-D acid, 891 g of diethanolamine and 30 g of Petro-Ag Special U.F. wetting agent or surfactant having a paste-like consistency and consisting of sodium mono- and dimethyl napthalene sulfonates, product of Petro Chemicals Corp., Fort Worth, Texas. A
heavy paste was formed on blending. The mixture was heated by running 94C water through the jacket of` the blender. After 14 minutes of heating and blending, the 31,494-F -12-_13_ ~ 7~
mixture changed color, consistency and reaction to ~orm the salt was judged to be complete.
Cooling was started by passing cold water through the jacket of the blender as blending of the paste was continued. After a solid was formed, continued mixing broke the lumps initially formed into a powder and 20 g of Sipernat 22 S~ (an absorptive silica) trademark of the Degusson Corporation, Teterboro, New Jersey, was added. About 38 percent of the product passed a 16 mesh (U.S. Sieve Series) sieve without resort to grinding. The sieved material dissolved readily in water at ambient temperature as shown by the fact 75 g of product dissolved in sufficient water to yield 100 ml of solution.
Example 13 Upon heating and agitating together in a beaker 250 g of picloram and 584 g of diethanolamine, a clear melt was obtained at a temperature of 70C. Meanwhile, 1000 g of 2,4-D and 20 g Petro Ag Special U.F. wetting agent were placed in a water jacketed blender and pre-mixed. The melt of reacted picloram and diethanolamine was added to the premix in the blender, and hot water was started through the jacket while blending was carried out. After 8 minutes the mixture had become a dark green melt with some lumpy material dispersed therein. Cooling was started by running cold water through the blender jacket while mixing continued.
After about l~ hours, the mixture had become a free-flowing powder. Then 20 g of Sipernat 22 S absortive silica was blended with the powder, and the resulting mixture was sieved through a 16 mesh sieve, oversized material being recycled for. lO minutes. A 75 percent 31,494-F -13--14~ 3~
fraction of the material passed through the sieve.
About 32 g of the ~sieved material was capable of dissolving in sufficient water to form 100 ml of solution.
Example 14 To a water jacketed blender was added 1400 g MCPA and 20 g Petro Ag Special U.F., and the two mixed while warm water was passed through the jacket. Then 426 g of monoethanolamine was added to the warmed mixture. Reaction was complete in 6 minutes as mixing continued, as shown by the formation of a melt. Cold water was started through the blender jacket and mixing was again continued. Within 20 minutes a free-flowing powder had formed which was blended with 20 g of added Sipernat 22 S silica. The powder product was subjected to sieving through a 16 mesh sieve with recycling.
About 79 percent of the product passed the screen, and 60 g of the sieved material was capable of dissol~ing in water at ambient temperature to form a 100 ml solution.
Example 15 In an initial run, an alkanolamine salt of 2,4-D was prepared by warming and mixing 44.2 g (0.2 mole) of 2,4-D and 21.0 g (0.2 rnole) of diethanolarnine together in an equimolar ratio in a water jacketed 3 blender. The paste initially formed turned into a melt as warming and mixing continued. Cooling water was then introduced into the jacket of the blender while stirring was continued. The melt solidified into lumps which rather readily broke up into a free-flowing powder.
31,494-F -14-_15- ~ 7 Example 16 In additional runs performed as in Example 15, the same amount of 2,4-D was used in each run, but part of the equimolar amount of diethanolamine was replaced, on an equal weight basis, by monoethanolamine. The extent of replacement varied from 2.5 to 20 percent whereby the number of moles of alkanolamine also varied. 274-D alkanolamine salt using the mixed alkanolamines was carried out employing the method described hereinabove for the diethanolamine salt.
Example 17 In the runs from Example 15 and 18, the melting range of the free-flowing powder product was determined. In addition in each case, 5 + 0.1 g of powder was measured out and placed in a 100 milliliter (ml) graduated cylinder. Deionized water having a temperature of 22C and a pH of 6.7 was added to each cylinder to bring the volume to 100 ml and the cylinder stoppered. The cylinder, in each case, was inverted manually each second in a uniform manner. After every' six inversions, the contents of the cylinder were inspected for undissolved solids, and the number of inversions required to obtain complete solution of the solids noted. The pH of the resulting solutions was determined with a conventional pH meter equipped with a combination glass electrode.
The results of the foregoing tests are summarized in the following Table 2:
31,494-F -15-~ ~3 ~ 7 Phvsical Properties of Combination Salt Products . , ~ , ,,, .~ __ N
NUoOn Substituted Temperature to Solution ~ ~ ____________ __~ __,___ 1 0 78.5 to 80.5 57 4.9 __ __ ~ ~ __ 2 2.577 to 78.5 52 6.5 . ., ~ _~_ ~
3 576 to 77 48 7.3 4 7.573.5 to 75 29 7.8 1 0 _ . _ ...... . _ 73 to 74O5 30 7.9 . ~ _._ _~
6 12.5 68 to 99 20 8.1 _ ~ _, ~ ~
7 5 67.5 to 103 ~ _8 B 2 8 20 66 to 108 5 8.4 _ _ Example 18 Using substantially the same procedure as set forth in Example 15 for mixed alkanolamine salts except that the amount of monoethanolamine substituted for diethanolamine was fixed at 10 percent by weight, mixed alkanolamine salts of 2,4-D and of picloram were prepared, respectively. A mixture was prepared by thoroughly blending together the two salts. The mixture containecl 5 moles of the 2,4-D salt per mole of the picloram salt.
Example l9 3o The procedure of Example 15 was also repeated, co-reacting a mixture of 2,4-D and picloram in a 5:1 molar ratio with a quantity of the mixed alkanolamine which would have been equimolar if it had been all diethanolamine. The alkanolamine mixture provided about 7 mole percent more alkanolamine than the same 31,494-F -16-~ 3 ~ 7 weight of diethanolamine provides~ The melting temperature, ease of solubility and pH of a 5 percent by weight aqueous solution of the dry blended mixture and co-reacted mixture were determined in the same manner as described in Example 15O The results are summarized as follows:-Properties of Mixed Alkanolamine Salts Run ilerbicide Meltin~ Inversions IPH of 5 lo No. Combination Temp. C To Solution Dissolve _~ ~ ___ 1 2,4-D + picloram 65 to 92 9 8.1 dry mixed . . __ _ . _ 2 2,4-D + picloram 58 to 90 20 8.1 co-reacted _ . ~
31,494-F -17-
According to another aspect of the present invention there is provided the method of preparing substantially water-free water-dispersible herbicidal product of a phenyl-, phenoxy- or oxobenzothiazolyl 2-propanoic acid or acetic acid herbicide which comprises:
(a) warming gradually while stirring, in the absence of a solvent medium, a substantially stoichiometric mixture of one or more of said herbicides and diethanolamine, said mixture having added thereto from about 7 to about 15 percent by weight oE
ethanolamine based on the weight of diethanolamine employed; and (b) continuing to warm and stir the mixture until a paste or incipient melt is formed;
(c) allowing the mixture to cool;
(d) continuing to stir the mixture as it cools until a free-flowing powder is obtained; and (e) dry blending the cooled powder with from about 0.2 to 2 percent by weight of an agriculturally acceptable sequestrant, from about 0.5 to about 2 percent by weight of an agriculturally g~
- 2a - 73776-11 accep-table surfactant and from about 0.5 to about 2 percent by weight of an anticaking agent.
The herbicide "2,4-D" refers to the compound known as (2~4-dichlorophenoxy~ acetic acid, a white crystalline solid, having a melting point o~ 135 to 138 Centigrade (C) (technical) and 140 to 141 (pure).
The herbicide "MCPA" refers to the compound known as metaxon or [(4-chloro-O-tolyl)oxy]acetic acid ~ ~ 3 which is a light brown solid having a melting point of 118~ to 119C (pure) or 99 to 107C (technical).
The herbicide "MCPP" refers to the compound known as mecoprop or [2-(2-methyl-4-chlorophenoxy)--propionic acid], which is a colorless crystalline solid having a melting point of 94 to 95C.
The herbicide "triclopyr" refers to the compound [(3,5,6-trichloro-2-pyridinyl)oxy]acetic acid having a melting point of 148 to 150C.
The herbicide "clopyralid" refers to the compound 3,6-dichloropicolinic acid or by code name DOWCO 290, of The Dow Chemical Company, Midland, Michigan. Clopyralid is a white, crystalline solid having a melting point of 151 to 152C.
The herbicide "picloram" refers to the compound 4-amino-3,5,6-trichloropicolinic acid, a white powder which decomposes before melting.
The herbicide "benazolin" refers to the compound 4-chloro-2-oxobenzothiazolin-3-ylacetic acid, which has a melting point of 189C.
The herbicide "dicamba" refers to the compound 3,6-dichloro-o-anisic acid, which is a white crystalline solid (reference grade) or a brown crystalline solid (technical acid) having a melting point of 114 to 116C.
The term "alkanolamine" is intended to mean any one or more of ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine or triisopropanolamine, which are capable of forming a 31,494-F -3-~ 7 crystalline salt of any of` sa.id herbicides which is a solid at room temperature.
The term "ethanol amine" (.MEA) refers to the compound known as ~-aminoethanol or 2-hydroxyethylamine having the formula HOCH2CH2NH2o The term "diethanolamine" (DEA) refers to the compound known as di(2-hydroxyethyl)amine having the formula (HOCH2CH2)2NH.
The term "triethanolamine" (TEA) refers to the compound known as tri(2-hydroxyethyl)amine having the formula (HOCH2CH2)3N.
The term "isopropanolamine" (MIPA) refers to the compound known as 2-hydroxypropylamine or 1-amino-2-propanol) having the formula CH3CH(OH)CH2NH2.
The term "diisopropanolamine" (DIPA) refers to the compound having the formula (CH3CHOHCH2)2NH.
The term "triisopropanolamine" refers to the compound having the formula N(C3H60H)3.
The alkanolamines are known compounds and can be prepared by reaction of ethyloxide and ammonium to give a mixture of mono-, di-, and triethanolamines.
Where diethanolamine and ethanolamine are jointly employed7 the proportions of diethanolamine to ethanolamine in the alkanolamine mixture can range from about 7 to about 15 percent by weight of ethanolamine, based on the total weight of diethanolamine, more preferably from about 7 to about 12 percent by weight based on the weight of the diethanolamine employed.
31,494-F -4-~ ~ 3 ~7 A preferred mixture of the alkanolamine is a 50:50 mixture by weight oP diethanolamine and ethanolamine.
In preparing the substantially water-free alkanolamine salt, quantities of the phenyl, phenoxy or oxobenzothiazolyl alkanoic acid herbicide are warmed gradually to a temperature at or below the melting temperature of the herbicide. To the warmed herbicide, a substantially~equimolar amount of an alkanolamine described hereinbefore is added. The mixture of the herbicide and alkanolamine is continuously warmed and stirred until a paste or an incipient melt is formed.
Upon formation of the paste or incipient melt, the mixture is allowed to cool, and the cooling mixture is stirred until a free-flowing powder is obtained. In general, the alkanolamine salts of the invention are freely water soluble. This is clearly preferred.
The alkanolamine salts prepared according to the invention have substantially the same herbicidal properties as the alkanGlamine salts prepared in aqueous or organic solvent reaction medium.
Optionally and preferably, sequestrants, surfactants and anticaking agents can be further admixed with the free-flowing powder to improve the handling and/or herbicidal efficacy properties of said herbicide compounds.
Agriculturally acceptable sequestrants include, but are not limited to, ethylenediamine tetraacetic acid, cLtric acid or a diglycolic acid. The amount of sequestrant added to the free-flowing powder can range 31,494-F -5-3~791 from about 0.2 to about 2 percent by weight of the final herbicide product.
Agriculturally acceptable surfactants or wetting agents include, but are not limited to, sodium9 mono- and dimethyl napthalene sulfonates. A preferred surfactant is Petro-Ag Special U.F., product of Petro Chemicals Corporation9 Fort Worth, Texas. The amount of surfactant added to the free-flowing powder can range from about 0.5 to about 2 percent by weight of the final herbicide product.
Agriculturally acceptable anticaking agents include, but are not limited to, fumed silica or hydrated reprecipitated silica. A preferred anticaking agent is Sipernat 22, trademark of the Degusson Corporation, Teterboro, New Jersey. The amount of anticaking agent addèd to the free-flowing powder can range from about 0.5 to about 2 percent by weight of the final herbicide product.
The sequestrants, surfactants and anticaking agents can be dry blended to the cooled powder to form the desired herbicide product.
The ~ollowing examples illustrate the present invention and the manner by which it can be practiced but, as such, should not be construed as limitations upon the overall scope of the same.
Example l On mixing 256.5 grams (g) (1.0 mole) of triclopyr ancl 105 grams (1.0 mole) of diethanolamine, a damp compressible powder was obtained. This mixture was warmed and stirred simultaneously. The mixture 31,494-F -6-~r~ 3~7~
~radually became paste-like and then, without ~orming a true melt, started to thickenO Heating was stopped but stirring was continuedO As the reaction mixture cooled it turned into a free-flowing powder that was readily soluble in water.
Example_2 A clear melt was made by gradually warming and stirring 44.2 g (0.2 mole) of 2,4-D with 2100 g (0.2 mole) of diethanolamine. On cooling and stirring the melt, the solid herbicide amine salt was obtained in free-flowing powder form.
Example 3 In a sïmilar manner, as in Example 2, a free-flowing powder was formed on reacting 24.1 g (0.10 mole) of picloram and 10.5 g (0.1 mole) of diethanolamine salt.
Example 4 A dry mixture was prepared by grinding 10 g of the 2,4-D amine salt as prepared in Example 2 and 2 g of the picloram amine as prepared in Example 3 together with a mortar and pestle until a uniform blend was obtained. The dry mixture was free-~lowing and readily water soluble. On applying an aqueous solution of the ary mixture to broadleaf weedy plants at a herbicidally effective rate, the expected spectrum of weedy planks is controlled to the extent predicted from known uses of the aeti~e ingredient amine salts separately applied.
31,494-F -7-Example 5 A 44.2 g (0.2 mole) portion of 2,4-D and 21.0 g (0.2 mole) of diethanolamine were reacted and made into a free-flowing powder in the same manner as described in Example 2.
Example 6 In a similar manner, as in Example 2, 43.0 g (0.2 mole) of mecoprop was reacted with 21.0 g (0.2 mole) of diethanolamine, and 22.0 g (0.10 mole) of dicamba was reacted with 10.5 g (0.10 mole) of diethanolamine, in both cases forming a free-flowing powder.
A dry mixture was then made by dry blending 26 g of the 2, 4-D salt, 13 g of t~e mecoprop salt and 2.5 g of the dicamba salt to form a useful, stable readily water soluble herbicidal mixture. On applying an aqueous solution of the three-component dry mixture to broadleaf weedy plants at a herbicidally effective rate the expected spectrum of weedy plants is controlled to the extent predicted from known uses of the active ingredient salts separately applied.
Example 7 Using the same procedures, as in Examples 2 and 5, 25.0 g of 3,6-dichloropicolinic acid were reacted with 13.7 g (0.13 mole) of diethanolamine and 25.0 g (0.10 mole) of benazolin were reacted with 10.8 g of (0.10 mole) of diethanolamine to form free-flowing salt powders. A 15 g portion of each salt powder was thoroughly dry blended together to provide a useful, stable, free-flowing freely water soluble herbicidal 31,494-F -8-~ 3~3 _9_ mixture. On applying an aqueous solution of the two-component mixture alone or with a small amount of surfactant added to broadlea~ weedy plants at a herbicidally effective rate, the expected spectrum of weedy plants is controlled to the extent predicted from known uses o.f the active ingredient salts separately applied.
Example A mixture of 14.0 g (0.06 mole) of picloram and 38.4 g (0.361 mole) of diethanolamine was warmed and stirred together until complete reaction of the picloram was shown by formation of a clear melt. Then 68.0 g (0.31 mole) of 2,4-D was added to the melt, and the melt stirred as it cooled, forming a free-flowing powder. The free-flowing powder was found to be readily water soluble. The herbicidal properties of the picloram and 2,4-D salts are substantially the same as that of the diethanolamine salts made in other ways.
Example 9 A mixture of 32.0 g (0.14 mole) of 2,4-D, 1~.0 g (0.07 mole) of mecoprop, 3.0 g (0.01 mole) of dicamba and 25.0 g (0.23 mole) of diethanolamine was gradually warmed and stirred together sufficiently to obtain a clear melt, then stirred while the melt cooled and turned into a free flowing powder. The co-reacted 3 salts so-prepared are readily water soluble, and the herbicidal properties are substantially not changed by the method of making the salts. The mixture is a useful herbicidal product that is conveniently and economically handled and transported.
31,494-F -9-~ o ~3~3'7~
Example 10 A mixture of 25.0 g (0.13 mole) of 3.6-dichloropicolinic acid (clopyralid) 9 25.0 g of benazolin (0.10 mole) and 24.5 g (0.23 mole) of diethanolamine was gradually warmed and stirred together sufficiently to obtain a clear melt, then stirred while the melt cooled into lumps which readily broke up on continued stirring to form a free-flowing powder. The co-reacted salts so-prepared are readily water soluble and the herbicidal properties are substantially not changed by the method of making the salts. The mixture is a useful herbicidal product that is conveniently and economically handled and transported.
Example 11 The diethanolamine salts of 2,4-D, mecoprop and dicamba are prepared separately by reacting 32.0 g of 2,4-D, 16.0 g of mecoprop and 3.0 g of dicamba with respective stoichiometric amounts of diethanolamine in the manner described in`Example 1, each forming a free-flowing powder. The so-obtained dry powders are thoroughly dry-blended together to form a useful herbicidal product that is readily water soluble.
The melting temperature of the blended powders was determined along with that of the combination 3 products of Examples 2, 7, 8, 9 and 10. Each combination product was passed through a 30 mesh sieve (U.S. Sieve Series) and the underflow used for ease of water solubility tests and pH determination of a 5 percent by weight aqueous solution of each combination product. From the sieved material, in each case, 5 +
31,494-F -lO-Z~3~
0.1 g of powder was measured out and placed in a lO0 milliliter (ml~ graduated cylinder. Deionized water having a temperature of 22C9 and a pH of 6.7 was added to each cylinder to bring the volume to 100 ml and the cylinder stoppered. The cylinder, in each case, was inverted manually each seco~d in a uniform manner.
After every six inversions, the contents of the cylinder were inspected for undissolved solids and the number of inversions required to obtain complete solution of the solids noted. The pH of the resulting solutions was determined with a conventional pH meter equipped with a combination glass electrode.
3o 31,494-F -ll-~2~3~7~
The results of the foregoing tests are summarized in the following Table 1:
_able 1 PHYSICAL PROPERTIES OF COMBINATION SALT PRODUCTS
, . . . n_ _ __ Comblnation Product Tempera- ¦nver- pH of 5%
____ _ _ A. 2,4-D ~ picloram _ _ . _ _ ._ . _ _ -Dry mixed salts 73.5 44 5.2 ~ _ ~ . _ -Co-reacted salts 74.5 50 4.8 _~ _ . ..
B. 2,4 D ~ mecoprop 1 ~ . . , _ ~ .
, -Dry mixed salts57 to 74 26 5.1 . _. . . __ -Co-reacted salts59 to 71 38 4.9 _ ~ _ , C. Clopyralid~benazolin ~_ . . . . .
-Dry mixed salts 118 to 20 7.4 _ -Co-reacted salts 110 to 28 7.4 Example 12 A water jacketed blender was charged with 1875 g of 2,4-D acid, 891 g of diethanolamine and 30 g of Petro-Ag Special U.F. wetting agent or surfactant having a paste-like consistency and consisting of sodium mono- and dimethyl napthalene sulfonates, product of Petro Chemicals Corp., Fort Worth, Texas. A
heavy paste was formed on blending. The mixture was heated by running 94C water through the jacket of` the blender. After 14 minutes of heating and blending, the 31,494-F -12-_13_ ~ 7~
mixture changed color, consistency and reaction to ~orm the salt was judged to be complete.
Cooling was started by passing cold water through the jacket of the blender as blending of the paste was continued. After a solid was formed, continued mixing broke the lumps initially formed into a powder and 20 g of Sipernat 22 S~ (an absorptive silica) trademark of the Degusson Corporation, Teterboro, New Jersey, was added. About 38 percent of the product passed a 16 mesh (U.S. Sieve Series) sieve without resort to grinding. The sieved material dissolved readily in water at ambient temperature as shown by the fact 75 g of product dissolved in sufficient water to yield 100 ml of solution.
Example 13 Upon heating and agitating together in a beaker 250 g of picloram and 584 g of diethanolamine, a clear melt was obtained at a temperature of 70C. Meanwhile, 1000 g of 2,4-D and 20 g Petro Ag Special U.F. wetting agent were placed in a water jacketed blender and pre-mixed. The melt of reacted picloram and diethanolamine was added to the premix in the blender, and hot water was started through the jacket while blending was carried out. After 8 minutes the mixture had become a dark green melt with some lumpy material dispersed therein. Cooling was started by running cold water through the blender jacket while mixing continued.
After about l~ hours, the mixture had become a free-flowing powder. Then 20 g of Sipernat 22 S absortive silica was blended with the powder, and the resulting mixture was sieved through a 16 mesh sieve, oversized material being recycled for. lO minutes. A 75 percent 31,494-F -13--14~ 3~
fraction of the material passed through the sieve.
About 32 g of the ~sieved material was capable of dissolving in sufficient water to form 100 ml of solution.
Example 14 To a water jacketed blender was added 1400 g MCPA and 20 g Petro Ag Special U.F., and the two mixed while warm water was passed through the jacket. Then 426 g of monoethanolamine was added to the warmed mixture. Reaction was complete in 6 minutes as mixing continued, as shown by the formation of a melt. Cold water was started through the blender jacket and mixing was again continued. Within 20 minutes a free-flowing powder had formed which was blended with 20 g of added Sipernat 22 S silica. The powder product was subjected to sieving through a 16 mesh sieve with recycling.
About 79 percent of the product passed the screen, and 60 g of the sieved material was capable of dissol~ing in water at ambient temperature to form a 100 ml solution.
Example 15 In an initial run, an alkanolamine salt of 2,4-D was prepared by warming and mixing 44.2 g (0.2 mole) of 2,4-D and 21.0 g (0.2 rnole) of diethanolarnine together in an equimolar ratio in a water jacketed 3 blender. The paste initially formed turned into a melt as warming and mixing continued. Cooling water was then introduced into the jacket of the blender while stirring was continued. The melt solidified into lumps which rather readily broke up into a free-flowing powder.
31,494-F -14-_15- ~ 7 Example 16 In additional runs performed as in Example 15, the same amount of 2,4-D was used in each run, but part of the equimolar amount of diethanolamine was replaced, on an equal weight basis, by monoethanolamine. The extent of replacement varied from 2.5 to 20 percent whereby the number of moles of alkanolamine also varied. 274-D alkanolamine salt using the mixed alkanolamines was carried out employing the method described hereinabove for the diethanolamine salt.
Example 17 In the runs from Example 15 and 18, the melting range of the free-flowing powder product was determined. In addition in each case, 5 + 0.1 g of powder was measured out and placed in a 100 milliliter (ml) graduated cylinder. Deionized water having a temperature of 22C and a pH of 6.7 was added to each cylinder to bring the volume to 100 ml and the cylinder stoppered. The cylinder, in each case, was inverted manually each second in a uniform manner. After every' six inversions, the contents of the cylinder were inspected for undissolved solids, and the number of inversions required to obtain complete solution of the solids noted. The pH of the resulting solutions was determined with a conventional pH meter equipped with a combination glass electrode.
The results of the foregoing tests are summarized in the following Table 2:
31,494-F -15-~ ~3 ~ 7 Phvsical Properties of Combination Salt Products . , ~ , ,,, .~ __ N
NUoOn Substituted Temperature to Solution ~ ~ ____________ __~ __,___ 1 0 78.5 to 80.5 57 4.9 __ __ ~ ~ __ 2 2.577 to 78.5 52 6.5 . ., ~ _~_ ~
3 576 to 77 48 7.3 4 7.573.5 to 75 29 7.8 1 0 _ . _ ...... . _ 73 to 74O5 30 7.9 . ~ _._ _~
6 12.5 68 to 99 20 8.1 _ ~ _, ~ ~
7 5 67.5 to 103 ~ _8 B 2 8 20 66 to 108 5 8.4 _ _ Example 18 Using substantially the same procedure as set forth in Example 15 for mixed alkanolamine salts except that the amount of monoethanolamine substituted for diethanolamine was fixed at 10 percent by weight, mixed alkanolamine salts of 2,4-D and of picloram were prepared, respectively. A mixture was prepared by thoroughly blending together the two salts. The mixture containecl 5 moles of the 2,4-D salt per mole of the picloram salt.
Example l9 3o The procedure of Example 15 was also repeated, co-reacting a mixture of 2,4-D and picloram in a 5:1 molar ratio with a quantity of the mixed alkanolamine which would have been equimolar if it had been all diethanolamine. The alkanolamine mixture provided about 7 mole percent more alkanolamine than the same 31,494-F -16-~ 3 ~ 7 weight of diethanolamine provides~ The melting temperature, ease of solubility and pH of a 5 percent by weight aqueous solution of the dry blended mixture and co-reacted mixture were determined in the same manner as described in Example 15O The results are summarized as follows:-Properties of Mixed Alkanolamine Salts Run ilerbicide Meltin~ Inversions IPH of 5 lo No. Combination Temp. C To Solution Dissolve _~ ~ ___ 1 2,4-D + picloram 65 to 92 9 8.1 dry mixed . . __ _ . _ 2 2,4-D + picloram 58 to 90 20 8.1 co-reacted _ . ~
31,494-F -17-
Claims (31)
1. Method of preparing substantially water-free alkanolamine salt of a herbicide which comprises:
(a) warming gradually while stirring in the absence of an added organic or aqueous medium a substantially equimolar mixture of one or more of said herbicides and an alkanolamine and continuing to warm and stir the mixture until a paste or incipient melt is formed;
(b) allowing the mixture to cool; and (c) continuing to stir the mixture as it cools until a free-flowing powder is obtained.
(a) warming gradually while stirring in the absence of an added organic or aqueous medium a substantially equimolar mixture of one or more of said herbicides and an alkanolamine and continuing to warm and stir the mixture until a paste or incipient melt is formed;
(b) allowing the mixture to cool; and (c) continuing to stir the mixture as it cools until a free-flowing powder is obtained.
2. The method of Claim 1 wherein the herbicide is 2,4-D, MCPA, MCPP, triclopyr, clopyralid, picloram, benazolin, dicamba, or a mixture of` any two or more of such herbicidal compounds.
3. The method of Clairn 1 wherein tne alkanolamine is any one or more of ethanolamine, 31,494-F -18-diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine or triisopropanolamine which are capable of forming a crystalline salt of any of said herbicides which is a solid at room temperature.
4. The method of Claim 3 carried out using any of the herbicides of Claim 2 which form solid salts with any of the alkanolamines of Claim 3.
5. The method of Claim 1 wherein the herbicide is 2,4-D and the alkanolamine is ethanolamine, diethanolamine or triethanolamine.
6. The method of Claim 1 wherein the herbicide is MCPA and the alkanolamine is ethanolamine.
7. The method of Claim 1 wherein the herbicide is triclopyr and the alkanolamine is ethanolamine or diethanolamine.
8. The method of Claim 1 wherein the herbicide is clopyralid and the alkanolamine is diethanolamine.
9. The method of Claim 1 wherein the herbicide is picloram and the alkanolamine is ethanolamine, diethanolamine, diisopropanolamine or triisopropanolamine.
10. The method of Claim 1 wherein the herbi-cide is MCPP and the alkanolamine is diethanolamine.
11. The method of Claim 1 wherein the herbi-cide is dicamba and the alkanolamine is diethanolamine.
31,494-F -19-
31,494-F -19-
12. The method of Claim 1 wherein the herbicide is benazolin and the alkanolamine is diethanolamine.
13. The method of Claim 1 wherein the herbicide is any one or more of 2,4-D, MCPP, triclopyr, clopyralid, picloram, dicamba or benazolin and the alkanolamine is diethanolamine.
14. The method of Claim 1 wherein the herbicide is a mixture of 2,4-D and picloram and the alkanolamine is diethanolamine.
15. The method of Claim l wherein the herbicide is a mixture of dicamba and MCPP and the alkanolamine is diethanolamine.
16. The method of Claim 1 wherein the herbicide is a mixture of 2,4-D, MCPP and clopyralid and the alkanolamine is diethanolamine.
17. The method of Claim 1 wherein the herbicide is a mixture of MCPA, MCPP and clopyralid and the alkanolamine is about a 50:50 mixture by weight of diethanolamine and ethanolamine.
18. The method of preparing a substantially water-free water dispersible herbicidal product of a phenyl, phenoxy or oxobenzothiazolyl alkanoic acid herbicide which comprises:
(a) warming gradually while stirring a substantially stoichiometric mixture of one or more of said herbicides and an alkanolamine in the absence of a solvent medium, and continuing to warm and stir the mixture until a paste or incipient melt is formed, 31,494-F -20-allowing the mixture to cool and continuing to stir the mixture until a free-flowing powder is obtained; and (b) dry blending the cooled powder with from about 0.2 to 2 percent by weight of an agriculturally acceptable sequestrant; from about 0.5 to about 2 percent by weight of an agriculturally acceptable surfactant and from about 0.5 to about 2 percent by weight of an anticaking agent.
(a) warming gradually while stirring a substantially stoichiometric mixture of one or more of said herbicides and an alkanolamine in the absence of a solvent medium, and continuing to warm and stir the mixture until a paste or incipient melt is formed, 31,494-F -20-allowing the mixture to cool and continuing to stir the mixture until a free-flowing powder is obtained; and (b) dry blending the cooled powder with from about 0.2 to 2 percent by weight of an agriculturally acceptable sequestrant; from about 0.5 to about 2 percent by weight of an agriculturally acceptable surfactant and from about 0.5 to about 2 percent by weight of an anticaking agent.
19. The method of Claim 18 wherein the sequestrant is ethylenediamine tetraacetic acid, citric acid or a diglycolic acid.
20. The method of Claim 18 wherein the surfactant is a mono-or dimethyl naphthalene sulfonate.
21. The method of Claim 18 wherein the anticaking agent is fumed silica or hydrated reprecipitated silica.
22. The method of Claim 18 wherein the herbicide is any one of 2,4-D, MPCA, MCPP, triclopyr, clopyralid, picloram, benazolin, dicamba or a mixture of any two or more of such herbicidal compounds.
23. The method of Claim 18 wherein the alkanolamine is any one or more of ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine or triisopropanolamine.
24. The method of Claim 1 wherein the alkanolamine is diethanolamine having admixed therewith from about 7 to about 15 percent by weight of ethanolamine, based on the total weight of diethanolamine.
25. The method as in Claim 24 wherein the herbicide is 2,4 D, MCPA, MCPP, triclopyr, clopyralid, picloram, benazolin, dicamba, or a mixture of any two or more of such herbicidal compounds.
26. The method as in Claim 24 wherein the amount of ethanolamine used is about 7 to about 12 percent by weight based on the weight of the diethanolamine employed.
27. The method of preparing substantially water-free water-dispersible herbicidal product of a phenyl-, phenoxy- or oxobenzothiazolyl 2-propanoic acid or acetic acid herbicide which comprises, (a) warming gradually while stirring, in the absence of a solvent medium, a substantially stoichiometric mixture of one or more of said herbicides and diethanolamine, said mixture having added thereto from about 7 to about 15 percent by weight of ethanolamine based on the weight of diethanolamine employed; and (b) continuing to warm and stir the mixture until a paste or incipient melt is formed;
(c) allowing the mixture to cool;
(d) continuing to stir the mixture as it cools until a free-flowing powder is obtained; and (e) dry blending the cooled powder with from about 0.2 to 2 percent by weight of an agriculturally acceptable sequestrant, from about 0.5 to about 2 percent by weight of an agriculturally acceptable surfactant and from about 0.5 to about 2 percent by weight of an anticaking agent.
(c) allowing the mixture to cool;
(d) continuing to stir the mixture as it cools until a free-flowing powder is obtained; and (e) dry blending the cooled powder with from about 0.2 to 2 percent by weight of an agriculturally acceptable sequestrant, from about 0.5 to about 2 percent by weight of an agriculturally acceptable surfactant and from about 0.5 to about 2 percent by weight of an anticaking agent.
28. The method of Claim 27 wherein the sequestrant is ethylenediamine tetraacetic acid, citric acid or a diglycolic acid.
29. The method of Claim 27 wherein the surfactant is a mono-ordimethyl naphthalene sulfonate.
30. The method as in Claim 27 wherein the anticaking agent is a fine particulate fumed or hydrated reprecipitated silica.
31. The method as in Claim 27 wherein at least one of the surfactant, the seyuestrant and the anticaking agent are incorporated into the mixture prior to the cooling thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000526348A CA1293974C (en) | 1986-12-29 | 1986-12-29 | Preparation of alkanolamine salts of carboxylic acid herbicides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000526348A CA1293974C (en) | 1986-12-29 | 1986-12-29 | Preparation of alkanolamine salts of carboxylic acid herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1293974C true CA1293974C (en) | 1992-01-07 |
Family
ID=4134646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000526348A Expired - Fee Related CA1293974C (en) | 1986-12-29 | 1986-12-29 | Preparation of alkanolamine salts of carboxylic acid herbicides |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1293974C (en) |
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| WO2011063312A3 (en) * | 2009-11-23 | 2012-01-19 | Dow Agrosciences Llc | Improved process for preparing soluble granules of salts of pyridine - carboxylic acids |
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