CA1049805A - Trifluralin-metribuzin emulsifiable concentrate - Google Patents
Trifluralin-metribuzin emulsifiable concentrateInfo
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- CA1049805A CA1049805A CA236,690A CA236690A CA1049805A CA 1049805 A CA1049805 A CA 1049805A CA 236690 A CA236690 A CA 236690A CA 1049805 A CA1049805 A CA 1049805A
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- metribuzin
- trifluralin
- percent
- xylene
- formulation
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Abstract
TRIFLURALIN-METRIBUZIN EMULSIFIABLE CONCENTRATE
Abstract of the Disclosure A stable emulsifiable concentrate formulation con-taining the herbicidal combination of a dinitroaniline and metribuzin has been discovered. It comprises 10-20% metribuzin and 15-30% trifluralin in a ratio of metribuzin to trifluralin of 1:1 to 1:2, 3-7% emulsifier, 8-20% hydroxylated solvent and 23-64% xylene. Heretofore, it was not possible to make a single formulation containing the combination of metribuzin and trifluralin except as a wettable powder. The formulation improves the ease and accuracy of handling and applying the herbicidal combination.
Abstract of the Disclosure A stable emulsifiable concentrate formulation con-taining the herbicidal combination of a dinitroaniline and metribuzin has been discovered. It comprises 10-20% metribuzin and 15-30% trifluralin in a ratio of metribuzin to trifluralin of 1:1 to 1:2, 3-7% emulsifier, 8-20% hydroxylated solvent and 23-64% xylene. Heretofore, it was not possible to make a single formulation containing the combination of metribuzin and trifluralin except as a wettable powder. The formulation improves the ease and accuracy of handling and applying the herbicidal combination.
Description
TRIFLURALIN-METRIBUZIN EMULSIFIABLE CONCENTRATE
This invention belong to the field of agri-cultural chemistry, and provides a new emulsifiable con-centrate formulation which contains a dinitroaniline herbicide, particularly trifluralin, and the triazine herbicide, metribuzin. Use of the new formulation facil-itates the handling and application of the herbicidal combination, because the farmer can assure himself of applying the correct ratio of the two herbicides by handling a single, easily measured liquid formulation.
The dinitroaniline herbicides, of which tri-fluralin (2,6-dinitro-N,N-dipropyl-a,a,a-trifluoro-_-toluidine) is particularly important, have been known since the early 1960's to be exceptionally useful preemergence herbicides (e.g., see U.S. Patents 3,257,190 and 3,403,180).
The dinitroanilines are widely used to kill or prevent the germination of a wide range of weeds, and have been found to be safe for use in many ornamental and economic crops.
Metribuzin [4-amino-6-(t-butyl)-3-methylthio-1,2,4-tri-. .
azin-5(4H)-onel is a relatively new herbicide which is useful for preemergence control of weeds in some of the same ~ crops, especially soybeans, in which the dinitroanilines are - used (see U.S. Patent 3,671,523). Because the weed spectra of the dinitroanilines and of metribuzin are complementary, combinations of metribuzin with various dinitroanilines have been found to be particularly useful.
The dinitroanilines have relatively low melting points and are quite soluble in aromatic solvents. Thus, they have been most advantageously formulated as liquid emulsifiable concentrates. Metribuzin has a high melting point and is quite insoluble, and has been usually formu-, .. . ..
1049805lated as a wettable powder.
It is quite possible, of course, to apply a dinitroaniline and metribuzin in combination by mixing the individual formulations of the two compounds in the spray tank. To do so requires the farmer to measure the liquid formulation, and also to weigh the solid wettable powder, as well as to provide a spray tank which is agitated sufficiently well to disperse the wettab~e powder. The separate handling of the two components creates a double risk of error and wa8tes time. Until now, however, it has not been possible to make a single formulation containing the combination except as a wettable powder, which is necessarily much more difficult to measure and disperse than liquid formulations.
Moreover, the low melting points of the dinitroanilines cause wettable powders to have relatively poor storage -. stability. -The present invention is a liquid herbicidal emulsifiable concentrate which comprises from about 10 to about 20 percent by weight of metribuzin; from about 15 to about 30 weight percent of a soluble dinitroaniline herbicide, of which trifluralin is preferred, provided that the ratio of the amount of metribuzin to the amount of the dinitro-aniline is from about 1:1 to about 1:2; from about 3 to , about 7 percent of emulsifier comprising amine salts of - alkylarylsulfonates and polyoxyethylene ethers; from about 8 to about 20 percent of a hydroxylated solvent chosen from the group consisting of 2-ethoxyethanol, 2-methoxyethanol, ethanol and methanol; and from about 23 to about 64 percent of xylene.
X-3836 -3- ;
'. ." .': --, . . ,: , , :., ,, , -:; . , .. - , : ~ -- . .. .. . .
Throughout this specification and claims, amounts of the ingredients of the formulations are described as percentages by weight. When ratios of the amounts of ingredients are described, the terms "ratio" and "parts"
refer to ratios by weight and parts by weight.
Percentages herein have been calculated on the assumption that the density of all of the formulations is 10 lbs./Imp. gal. The assumption is quite accurate since the actual density of the formulations will be found to be in the range of about 9.8 to 10.2 lbs./Imp. gal.
The dinitroanilines which are referred to herein are those of the formula ' . ~ R2 ~, ,, N~
0~
.~
- R
, , .
wherein R represents methyl, isopropyl, t-butyl or tri-fluoromethyl, and Rl and R2 independently represent ethyl, propyl, allyl or 2-methylallyl. Such compounds are now :
- widely known in the agricultural chemical art. The fol--.~
lowing exemplary dinitroanilines are typical.
N-ethyl-2,6-dinitro-N-propylcumidine N,N-diallyl-2,6-dinitro-~-toluidine N-(2-methylallyl)-2,6-dinitro-N-propyl-a,~,~-trifluoro-~-toluidine
This invention belong to the field of agri-cultural chemistry, and provides a new emulsifiable con-centrate formulation which contains a dinitroaniline herbicide, particularly trifluralin, and the triazine herbicide, metribuzin. Use of the new formulation facil-itates the handling and application of the herbicidal combination, because the farmer can assure himself of applying the correct ratio of the two herbicides by handling a single, easily measured liquid formulation.
The dinitroaniline herbicides, of which tri-fluralin (2,6-dinitro-N,N-dipropyl-a,a,a-trifluoro-_-toluidine) is particularly important, have been known since the early 1960's to be exceptionally useful preemergence herbicides (e.g., see U.S. Patents 3,257,190 and 3,403,180).
The dinitroanilines are widely used to kill or prevent the germination of a wide range of weeds, and have been found to be safe for use in many ornamental and economic crops.
Metribuzin [4-amino-6-(t-butyl)-3-methylthio-1,2,4-tri-. .
azin-5(4H)-onel is a relatively new herbicide which is useful for preemergence control of weeds in some of the same ~ crops, especially soybeans, in which the dinitroanilines are - used (see U.S. Patent 3,671,523). Because the weed spectra of the dinitroanilines and of metribuzin are complementary, combinations of metribuzin with various dinitroanilines have been found to be particularly useful.
The dinitroanilines have relatively low melting points and are quite soluble in aromatic solvents. Thus, they have been most advantageously formulated as liquid emulsifiable concentrates. Metribuzin has a high melting point and is quite insoluble, and has been usually formu-, .. . ..
1049805lated as a wettable powder.
It is quite possible, of course, to apply a dinitroaniline and metribuzin in combination by mixing the individual formulations of the two compounds in the spray tank. To do so requires the farmer to measure the liquid formulation, and also to weigh the solid wettable powder, as well as to provide a spray tank which is agitated sufficiently well to disperse the wettab~e powder. The separate handling of the two components creates a double risk of error and wa8tes time. Until now, however, it has not been possible to make a single formulation containing the combination except as a wettable powder, which is necessarily much more difficult to measure and disperse than liquid formulations.
Moreover, the low melting points of the dinitroanilines cause wettable powders to have relatively poor storage -. stability. -The present invention is a liquid herbicidal emulsifiable concentrate which comprises from about 10 to about 20 percent by weight of metribuzin; from about 15 to about 30 weight percent of a soluble dinitroaniline herbicide, of which trifluralin is preferred, provided that the ratio of the amount of metribuzin to the amount of the dinitro-aniline is from about 1:1 to about 1:2; from about 3 to , about 7 percent of emulsifier comprising amine salts of - alkylarylsulfonates and polyoxyethylene ethers; from about 8 to about 20 percent of a hydroxylated solvent chosen from the group consisting of 2-ethoxyethanol, 2-methoxyethanol, ethanol and methanol; and from about 23 to about 64 percent of xylene.
X-3836 -3- ;
'. ." .': --, . . ,: , , :., ,, , -:; . , .. - , : ~ -- . .. .. . .
Throughout this specification and claims, amounts of the ingredients of the formulations are described as percentages by weight. When ratios of the amounts of ingredients are described, the terms "ratio" and "parts"
refer to ratios by weight and parts by weight.
Percentages herein have been calculated on the assumption that the density of all of the formulations is 10 lbs./Imp. gal. The assumption is quite accurate since the actual density of the formulations will be found to be in the range of about 9.8 to 10.2 lbs./Imp. gal.
The dinitroanilines which are referred to herein are those of the formula ' . ~ R2 ~, ,, N~
0~
.~
- R
, , .
wherein R represents methyl, isopropyl, t-butyl or tri-fluoromethyl, and Rl and R2 independently represent ethyl, propyl, allyl or 2-methylallyl. Such compounds are now :
- widely known in the agricultural chemical art. The fol--.~
lowing exemplary dinitroanilines are typical.
N-ethyl-2,6-dinitro-N-propylcumidine N,N-diallyl-2,6-dinitro-~-toluidine N-(2-methylallyl)-2,6-dinitro-N-propyl-a,~,~-trifluoro-~-toluidine
2,6-dinitro-N,N-dipropylcumidine 2,6-dinitro-N,N-dipropyl-~-toluidine 4-~t-butyl)-2,6-dinitro-N,N-dipropylaniline .. . . - - ~ . , .
.
.
10498al5 N-ethyl-N-(2-methylallyl)-2,6-dinitro-a,a,a-trifluoro-_-toluidine The preferred dinitroaniline is trifluralin, - 2,6-dinitro-N,N-dipropyl-a,~,a-trifluoro-_-toluidine.
The ratio of the amounts of metribuzin and of the dinitroaniline is fixed by the desired ratio of application rates. In general, the application ratios range from about one part of metrabuzin per about one part of dinitroaniline, to about one part of metribuzin per about two parts of dinitroaniline. The preferred ratio in most soil textures is about 2:3. These ratios reflect the usual application rates of thé herbicidal components when applied in com-bination.
For example, application rates of about 1/2 lb. of metribuzin and about 3/4 lb. of dinitroaniline per acre provide excellent weed control in some medium-textured 80il5. Rates of about 1/2 lb. of metribuzin and 1/2 lb. of dinitroaniline per acre are also frequently useful. In other circumstances, application rates in the range of about 1~2 lb. of metribuzin and 1 lb. of trifluralin or other dinitroaniline herbicide are the preferred rates.
Thus, those skilled in agricultural chemical formulation will understand that the ratio between the amounts of the herbicidal components is chosen according to the most widely used ratio of the components in the area for which the product is to be formulated. When a product is to be formulated for use across a wide geographic area, the .
preferred ratio of about 2 parts of metribazin to about 3 parts of the dinitroaniline is most generally desirable.
-~
X-3836 _5_ , . - . , . - . .......................... . : .
;, ~ .
104g805 The concentrations of the herbicidal components in the formulations are chosen entirely on the basis of convenience, within the limits set by the solubilities of the components. For convenience of the grower, the formu-lations should contain a unitary, or easily multiplied fractional, number of pounds of each herbicide per Imperial gallon. The solubilities of the herbicidal components allow a maximum total concentration of about 40-50 percent of combined herbicidal components. Thus, if a ratio of the herbicidal components of 1:2 is needed, for example, the I formulation most conveniently contains 1-1/2 lbs./Imp. gal.
- (15%) of metribuzin and 3 lbs./Imp. gal. (30~) of dinitro-aniline. For a ratio of 2:3, the formulation conveniently contains 1-1/2 lbs. of metribuzin (15%) and 2-1/4 lbs. of the dinitroaniline ~23%) per Imp. gal., and for a ratio of 1:1, the formulation best contains 2 lbs. of metribuzin (20~) and 2 lbs. of dinitroaniline (20%) per Imp. gal.
j A skilled agricultural chemical formulator will ;~l understand without further explanation that emulsifiable `~ 20 concentrates of this invention can be made which contain an ; infinite number of different ratios of the two herbicidal ,, , ` components. The range of ratios here named, from about 1:1 , to about 1:2, is believed to contain the most useful ratios.
~! It is recognized, however, that there may be soil types and climatic conditions which will require the herbicidal aomponents to be applied at different ratios. Should it be necessary to prepare a formulation according to this invention for such a condition, a skilled formulator can readily work out the most convenient concentrations of the herbicidal components to provide the desired ratio of the , - . . .. : .
: ::: .
. .
1~)49805 ~
components, given the guidance of this disclosure.
~; - Similarly, the named amounts of the herbicidal components, from about 10 to about 20 percent of metribuzin and from about 15 to about 30 percent of the dinitroaniline, k Will be found to describe all of the most widely usefulformulae for the formulations. Because of the need to maximize the concentration of the herbicidal components, for the sake of economy of inert ingredients, packaging and - freight costs, and also because of the limited solubility of 10 metribuzin, it will be only rarely that a formulation will most advantageously contain amounts of herbicidal components outside the named ranges of percentages.
Emulsifiers for agricultural emulsifiable con-centrates are available in great number and enormous variety. Formulators expect to find that any of many different emulsifiers can be used for a given formulation.
Such emulsifiers usually comprise mixtures of anionic and ' ~3 nonionic surfactants. The most advantageous emulsifier for the present formulations is a combination of amine salts of 20 alkylarylsulfonates, which provide the anionic portion of the emulsifier, and of polyoxyethylene ethers, which provide ~; .
the nonionic portion.
Throughout this specification and claims, the term "emulsifier", when not otherwise modified, will refer to the ~ above mixture of amine salts of alkylarylsulfonates and -- polyoxyethylene ethers.
The most highly preferred emulsifier is a com-bination of Emcol N-300B and Emcol N-500B, which are trade-marked products of Witco Chemical Corp., 277 Park Avenue, New York, New York.
- X-3~36 -7-.
' .
~,,, . , , ~ , , .; , . ., ~
The best results have been obtained by the use of Emcol N-300B and N-500B in ratios from about 4:6 to about 1:9. The most preferred ratio is about 2:8. However, ratios of the two surfactants from about 8:2 to about 1:9 have been found to be satisfactory in different instances.
The amount of emulsifier is usually from about 3 to about 7 percent, and the preferred amount is about 5 percent.
While the emulsifier named above is preferred, other emulsifiers are often satisfactory. For example, other useful anionic emulsifiers include alkylarylsulfonates and alkali and alkaline earth metal salts thereof, alkyl sulfates and salts thereof, naphthalenesulfonates, sul-fosuccinates, alkyl esters of sulfosuccinic acids, and aminated sulfates such as alkyl taurates. Suitable nonionic emulsifiers include polyoxyethylene sorbitan esters, esters ~ of fatty and resin acids such as sorbitan monolaurates, - sorbitan stearates and the like, glyseride esters such as ` glyceryl monooleate and the like, alkylarylpolyoxyethanols such as nonylphenylpolyethoxyethanol, ethoxylated alcohols, and glycol esters such as polyethylene glycol stearate.
- The solvent system of the formulations is a mixture of a hydroxylated solvent and xylene. The preferred hydroxylated solvent is 2-ethoxyethanol, but other alcohols such as ethanol, methanol and 2-methoxyethanol are also satisfactory. The optimum amount of the hydroxylated solvent will be found to be in the range of from about 8 to about 20 percent, and the preferred amount is about 15 percent. The hydroxylated solvent increases the solvency of the formulation to keep the metribuzin dissolved at low temperatures, and a formulator will find that the exact X-3~36 -8-, : . ~ . , ;' :: , ~ i ~ . .
.. . . .
1049~3~5 adjustment of the optimum economical amount of hydroxylated solvent follows the normal procedures of his art.
Xylene makes up the residue of the formulation, and its exact amount is fixed by the amounts of the other ingredients. For example, if it is necessary to increase the amount of one of the herbicidal components because it is somewhat impure, the amount of xylene is decreased by a corresponding amount.
Agricultural xylene is a mixture of the three isomers of xylene, ethylbenzene, and Cg aromatics such as trimethylbenzene, ethyltoluene and the like. Any of such compounds individually are ade~uate aromatic solvents for the present formulation, and mixtures of them are likewise perfectly satisfactory. The term "xylene" is used herein to refer to mixtures of xylenes and other C8-Cg alkylbenzenes, as well as to any of the components thereof individually. -The following specific examples are provided to assure that formulators fully understand the present invention.
Example 1 .~--15~ metribuzin 25% trifluralin 1% Emcol N-300B
4% Emcol N-500B
8~ 2-ethoxyethanol 47~ xylene Example _ -10% metribuzin -20% N-ethyl-N-(2-methylallyl)-2,6-dinitro a,a,a-trifluoro-_-toluidine X-3836 _9_ 2% Emcol N-300B
.
.
10498al5 N-ethyl-N-(2-methylallyl)-2,6-dinitro-a,a,a-trifluoro-_-toluidine The preferred dinitroaniline is trifluralin, - 2,6-dinitro-N,N-dipropyl-a,~,a-trifluoro-_-toluidine.
The ratio of the amounts of metribuzin and of the dinitroaniline is fixed by the desired ratio of application rates. In general, the application ratios range from about one part of metrabuzin per about one part of dinitroaniline, to about one part of metribuzin per about two parts of dinitroaniline. The preferred ratio in most soil textures is about 2:3. These ratios reflect the usual application rates of thé herbicidal components when applied in com-bination.
For example, application rates of about 1/2 lb. of metribuzin and about 3/4 lb. of dinitroaniline per acre provide excellent weed control in some medium-textured 80il5. Rates of about 1/2 lb. of metribuzin and 1/2 lb. of dinitroaniline per acre are also frequently useful. In other circumstances, application rates in the range of about 1~2 lb. of metribuzin and 1 lb. of trifluralin or other dinitroaniline herbicide are the preferred rates.
Thus, those skilled in agricultural chemical formulation will understand that the ratio between the amounts of the herbicidal components is chosen according to the most widely used ratio of the components in the area for which the product is to be formulated. When a product is to be formulated for use across a wide geographic area, the .
preferred ratio of about 2 parts of metribazin to about 3 parts of the dinitroaniline is most generally desirable.
-~
X-3836 _5_ , . - . , . - . .......................... . : .
;, ~ .
104g805 The concentrations of the herbicidal components in the formulations are chosen entirely on the basis of convenience, within the limits set by the solubilities of the components. For convenience of the grower, the formu-lations should contain a unitary, or easily multiplied fractional, number of pounds of each herbicide per Imperial gallon. The solubilities of the herbicidal components allow a maximum total concentration of about 40-50 percent of combined herbicidal components. Thus, if a ratio of the herbicidal components of 1:2 is needed, for example, the I formulation most conveniently contains 1-1/2 lbs./Imp. gal.
- (15%) of metribuzin and 3 lbs./Imp. gal. (30~) of dinitro-aniline. For a ratio of 2:3, the formulation conveniently contains 1-1/2 lbs. of metribuzin (15%) and 2-1/4 lbs. of the dinitroaniline ~23%) per Imp. gal., and for a ratio of 1:1, the formulation best contains 2 lbs. of metribuzin (20~) and 2 lbs. of dinitroaniline (20%) per Imp. gal.
j A skilled agricultural chemical formulator will ;~l understand without further explanation that emulsifiable `~ 20 concentrates of this invention can be made which contain an ; infinite number of different ratios of the two herbicidal ,, , ` components. The range of ratios here named, from about 1:1 , to about 1:2, is believed to contain the most useful ratios.
~! It is recognized, however, that there may be soil types and climatic conditions which will require the herbicidal aomponents to be applied at different ratios. Should it be necessary to prepare a formulation according to this invention for such a condition, a skilled formulator can readily work out the most convenient concentrations of the herbicidal components to provide the desired ratio of the , - . . .. : .
: ::: .
. .
1~)49805 ~
components, given the guidance of this disclosure.
~; - Similarly, the named amounts of the herbicidal components, from about 10 to about 20 percent of metribuzin and from about 15 to about 30 percent of the dinitroaniline, k Will be found to describe all of the most widely usefulformulae for the formulations. Because of the need to maximize the concentration of the herbicidal components, for the sake of economy of inert ingredients, packaging and - freight costs, and also because of the limited solubility of 10 metribuzin, it will be only rarely that a formulation will most advantageously contain amounts of herbicidal components outside the named ranges of percentages.
Emulsifiers for agricultural emulsifiable con-centrates are available in great number and enormous variety. Formulators expect to find that any of many different emulsifiers can be used for a given formulation.
Such emulsifiers usually comprise mixtures of anionic and ' ~3 nonionic surfactants. The most advantageous emulsifier for the present formulations is a combination of amine salts of 20 alkylarylsulfonates, which provide the anionic portion of the emulsifier, and of polyoxyethylene ethers, which provide ~; .
the nonionic portion.
Throughout this specification and claims, the term "emulsifier", when not otherwise modified, will refer to the ~ above mixture of amine salts of alkylarylsulfonates and -- polyoxyethylene ethers.
The most highly preferred emulsifier is a com-bination of Emcol N-300B and Emcol N-500B, which are trade-marked products of Witco Chemical Corp., 277 Park Avenue, New York, New York.
- X-3~36 -7-.
' .
~,,, . , , ~ , , .; , . ., ~
The best results have been obtained by the use of Emcol N-300B and N-500B in ratios from about 4:6 to about 1:9. The most preferred ratio is about 2:8. However, ratios of the two surfactants from about 8:2 to about 1:9 have been found to be satisfactory in different instances.
The amount of emulsifier is usually from about 3 to about 7 percent, and the preferred amount is about 5 percent.
While the emulsifier named above is preferred, other emulsifiers are often satisfactory. For example, other useful anionic emulsifiers include alkylarylsulfonates and alkali and alkaline earth metal salts thereof, alkyl sulfates and salts thereof, naphthalenesulfonates, sul-fosuccinates, alkyl esters of sulfosuccinic acids, and aminated sulfates such as alkyl taurates. Suitable nonionic emulsifiers include polyoxyethylene sorbitan esters, esters ~ of fatty and resin acids such as sorbitan monolaurates, - sorbitan stearates and the like, glyseride esters such as ` glyceryl monooleate and the like, alkylarylpolyoxyethanols such as nonylphenylpolyethoxyethanol, ethoxylated alcohols, and glycol esters such as polyethylene glycol stearate.
- The solvent system of the formulations is a mixture of a hydroxylated solvent and xylene. The preferred hydroxylated solvent is 2-ethoxyethanol, but other alcohols such as ethanol, methanol and 2-methoxyethanol are also satisfactory. The optimum amount of the hydroxylated solvent will be found to be in the range of from about 8 to about 20 percent, and the preferred amount is about 15 percent. The hydroxylated solvent increases the solvency of the formulation to keep the metribuzin dissolved at low temperatures, and a formulator will find that the exact X-3~36 -8-, : . ~ . , ;' :: , ~ i ~ . .
.. . . .
1049~3~5 adjustment of the optimum economical amount of hydroxylated solvent follows the normal procedures of his art.
Xylene makes up the residue of the formulation, and its exact amount is fixed by the amounts of the other ingredients. For example, if it is necessary to increase the amount of one of the herbicidal components because it is somewhat impure, the amount of xylene is decreased by a corresponding amount.
Agricultural xylene is a mixture of the three isomers of xylene, ethylbenzene, and Cg aromatics such as trimethylbenzene, ethyltoluene and the like. Any of such compounds individually are ade~uate aromatic solvents for the present formulation, and mixtures of them are likewise perfectly satisfactory. The term "xylene" is used herein to refer to mixtures of xylenes and other C8-Cg alkylbenzenes, as well as to any of the components thereof individually. -The following specific examples are provided to assure that formulators fully understand the present invention.
Example 1 .~--15~ metribuzin 25% trifluralin 1% Emcol N-300B
4% Emcol N-500B
8~ 2-ethoxyethanol 47~ xylene Example _ -10% metribuzin -20% N-ethyl-N-(2-methylallyl)-2,6-dinitro a,a,a-trifluoro-_-toluidine X-3836 _9_ 2% Emcol N-300B
3% Emcol N-500B
10% 2-methoxyethanol 55% xylene r Exam~le 3 15~ metribuzin 30% trifluralin
10% 2-methoxyethanol 55% xylene r Exam~le 3 15~ metribuzin 30% trifluralin
- 4~ emulsifier 11~ ethanol ., 10 40% xylene Example 4 15% metribuzin 15% 2,6-dinitro-N,N-dipropyl-_-toluidine 6% emulsifier 9% methanol 55% xylene ~, Example 5 12~ metribuzin :
24% 2,6-dinitro-N,N-dipropylcumidine 6% emulsifier 9% 2-methoxyethanol 49% xylene Example 6 -, 12% metribuzin ~::
. 20~ trifluralin ~ :
1.5% Emcol N-300B ~ -.
~; 3.5% Emcol N-500B
9% 2-ethoxyethanol ;
54~ xylene :
; X-3836 -10-1 ' :
ExamE~e 7 10% metribuzin 15% trifluralin : 1% Emcol N-300B
4% Emcol N-500B
15% 2-ethQxyethanol 55% xylene Example 8 10% metribuzin 18% N-ethyl-2,6-dinitro-N-propylcumidine ~ .
. 3% Emcol N-300B
3% Emcol N-500B
20% ethanol ~i.
46% xylene j Exam~ e 9 .'! 20% metribuzin 20% N,N-diallyl-2,6-dinitro-~-toluidine .
7% emulsifier :
s 10~ 2-methoxyethanol 43~ xylene Example 10 16% metribuzin 20% N-(2-methylallyl)-2,6-dinitro-N-propyl-a,a,a-trifluoro-~-toluidine 6.5% emulsifer 18% methanol 39.5% xylene Example 11 12% metribuzin 24% N-(t-butyl)-2,6-dinitro-N,N-dipropyl aniline - , . ,.
. .
.
, .
. 3.5% Emcol N-300B
. 1.5% Emcol N-SOOB
15% methanol 44% xylene Example 12 10% metribuzin - -20~ N-ethyl-N-(2-methylallyl)-2,6-dinitro a,a,a-trifluoro-p-toluidine 2.4% Emcol N-300B
I 1.6% Emcol N-500B
': 10 . . 12% ethanol 54~ xylene Example 13 15% metribuzin 20~ 2,6-dinitro-N,N-dipropylcumidine 3% emulsifier 10% 2-ethoxyethanol 52% xylene . :
. Example 14 : 20% metribuzin .` 20 30% trifluralin ;
24% 2,6-dinitro-N,N-dipropylcumidine 6% emulsifier 9% 2-methoxyethanol 49% xylene Example 6 -, 12% metribuzin ~::
. 20~ trifluralin ~ :
1.5% Emcol N-300B ~ -.
~; 3.5% Emcol N-500B
9% 2-ethoxyethanol ;
54~ xylene :
; X-3836 -10-1 ' :
ExamE~e 7 10% metribuzin 15% trifluralin : 1% Emcol N-300B
4% Emcol N-500B
15% 2-ethQxyethanol 55% xylene Example 8 10% metribuzin 18% N-ethyl-2,6-dinitro-N-propylcumidine ~ .
. 3% Emcol N-300B
3% Emcol N-500B
20% ethanol ~i.
46% xylene j Exam~ e 9 .'! 20% metribuzin 20% N,N-diallyl-2,6-dinitro-~-toluidine .
7% emulsifier :
s 10~ 2-methoxyethanol 43~ xylene Example 10 16% metribuzin 20% N-(2-methylallyl)-2,6-dinitro-N-propyl-a,a,a-trifluoro-~-toluidine 6.5% emulsifer 18% methanol 39.5% xylene Example 11 12% metribuzin 24% N-(t-butyl)-2,6-dinitro-N,N-dipropyl aniline - , . ,.
. .
.
, .
. 3.5% Emcol N-300B
. 1.5% Emcol N-SOOB
15% methanol 44% xylene Example 12 10% metribuzin - -20~ N-ethyl-N-(2-methylallyl)-2,6-dinitro a,a,a-trifluoro-p-toluidine 2.4% Emcol N-300B
I 1.6% Emcol N-500B
': 10 . . 12% ethanol 54~ xylene Example 13 15% metribuzin 20~ 2,6-dinitro-N,N-dipropylcumidine 3% emulsifier 10% 2-ethoxyethanol 52% xylene . :
. Example 14 : 20% metribuzin .` 20 30% trifluralin ;
5.6% Emcol N-500B
1.4% Emcol N-300B
. 20% 2-ethoxyethanol 23% xylene Formulation according to this invention have been found to be stable in low-temperature storage. Tests have ~ been applied in which the formulations were stored for :~
extended periods at 4.4C. and in a freezer at -17.2 to . --15.5C. The following formulations, for example, have been '', - . .,: - ,, , . ................. . . , ' :. .. . . ~ ,. . , , :
; tested under such conditions with the results reported below. The formulations below were made with technical metribuzin and technical trifluralin having purities of about 95 percent, and the amounts reflect overages to compensate for the impurities.
Example 15 12.6% metribuzin 25.2% trifluralin 1% Emcol N-300B
4% Emcol N-500B
8% 2-ethoxyethanol 49.2% xylene ; No precipitation of this formulation occurred when it was stored at 4.4C. for 60 days. Some precipitation occurred on the fourth day of storage in the freezer.
Example 16 12.6% metribuzin 25.2% trifluralin 1~ Emcol N-300B
.~ , 4% Emcol N-SOOB
10% 2-ethoxyethanol 47.2% xylene No precipitation occurred in 2 months of storage at 4.4C. In the freezer, the product precipitated between the 45th and 60th day of storage.
, The data above demonstrate that formulations of ~' this invention are unexpectedly stable in low-temperature storage. The stability shown is sufficient to permit ' ~ ..
formulations to be shipped and stored without special facilities. It is quite surprising to find that these :
'.
, . .
:. , . : , . , 10498~5 ~
liquid formulations are stable, in view of the known low solubility of metribuzin.
Formulations according to the present invention -have excellent emulsion stability, which is, of course, necessary in order that the formulation can be homogeneously dispersed in water and evenly applied. The emulsion stability has been evaluated by making emulsions of typical formulations in waters of hardness ranging from soft water of 57 ppm. hardness content to very hard water of 1026 ppm.
hardness, and allowing the emulsions to stand at room temperature for 4 hours. The example below shows a typical result.
Example 17 Formulations of this invention were made as follows: -12.6% metribuzin 25.2% trifluralin 10.6% 2-ethoxyethanol 46.6~ xylene 5% Emcol N-300B/N-500B
Formulations were made up in which the ratio of Emcol N-300B and N-500B was varied over a wide range. The emulsion tests were performed by adding 1 ml. of formulation to 100 ml. of water, at room temperature, in a 100 ml.
conical-bottom centrifuge tube. The tube was stoppered and inverted gently a few times to mix the emulsion and was then ; set upright and left undisturbed for 4 hours.
The formulations in which the ratio of emulsifiers was from 4:6 to 2:8 exhibited no instability of the emul-sions in any water over the 4-hour observation period. The ., ,:
10 49~30 5 formulation in which the ratio was 1:9 showed an unmea-surable trace of creaming at the bottom of the observation tube, and the formulation in which the ratio was 5:5 allowed only 0.1 ml. of cream to separate. The formulations in which the ratio of emulsifiers was from 8:2 to 6:4 allowed from no separation to 0.5 ml. of separated cream in the softest water, and allowed only about 0.3 ml. of oil to separate in the hardest water.
Example 18 ~ .
A formulation was made as follows:
- 15.5% metribuzin 23.3% trifluralin 4.0% Emcol N-500B
.. ..
1.0% Emcol N-300B
15.0% 2-ethoxyethanol 41.2% xylene Emulsion stability was tested as described above.
All of the emulsion samples were perfectly stable for 4 ' hours; no separation of the emulsions occurred in any water.
Samples were stored at -5C. for two weeks without precipitation. Precipitation occurred at -19C. after one week of storage; the precipitate redissolved upon warming to -5C.
!
Example 19 The following formulation was prepared:
,, :
16.1% metribuzin ' 21.4% trifluralin 4.0% Emcol N-SOOB -~
1.0% Emcol N-300B
15.0% 2-ethoxyethanol , ' , - - - . - .
.... .. ~
.
': . ' ' ' . '' ~ ' ' ': ' .~ . - . . . . .
42.5% xylene The emulsion sample of this product, also, was stable for 4 hours in all types of water.
; No precipitation of the product occurred in low-temperature storage at -5C. for two weeks. Storage at -19C., however, caused the product to precipitate within a few days.
The manufacture of the formulations is simple.
Only a simple liquid mixing tank, equipped with a low-- 10 powered agitator such as a propeller or a baffled turbine agitator, is necessary. No heating equipment is necessary, although the solvent or the mixture as a whole can be warmed, if desired, to speed the dissolution of the metri-buzin.
The formulations are used according to the normal methods of agricultural chemistry. The proper amount of the formulation to treat an acre of land is emulsified in from about 10 to about 50 gallons of water, depending on the type of application equipment in use, and applied evenly to the soil. Any of the many types of equipment in use for the application of soil-applied agricultural chemicals is perfectly satisfactory for applying the formulations of this ~ ~
invention. ~ --', ~
.
,, , , : ~
., . , . - . ... . .. .. .. . ..
, : .. : : , , :
, . . . . . . .
1.4% Emcol N-300B
. 20% 2-ethoxyethanol 23% xylene Formulation according to this invention have been found to be stable in low-temperature storage. Tests have ~ been applied in which the formulations were stored for :~
extended periods at 4.4C. and in a freezer at -17.2 to . --15.5C. The following formulations, for example, have been '', - . .,: - ,, , . ................. . . , ' :. .. . . ~ ,. . , , :
; tested under such conditions with the results reported below. The formulations below were made with technical metribuzin and technical trifluralin having purities of about 95 percent, and the amounts reflect overages to compensate for the impurities.
Example 15 12.6% metribuzin 25.2% trifluralin 1% Emcol N-300B
4% Emcol N-500B
8% 2-ethoxyethanol 49.2% xylene ; No precipitation of this formulation occurred when it was stored at 4.4C. for 60 days. Some precipitation occurred on the fourth day of storage in the freezer.
Example 16 12.6% metribuzin 25.2% trifluralin 1~ Emcol N-300B
.~ , 4% Emcol N-SOOB
10% 2-ethoxyethanol 47.2% xylene No precipitation occurred in 2 months of storage at 4.4C. In the freezer, the product precipitated between the 45th and 60th day of storage.
, The data above demonstrate that formulations of ~' this invention are unexpectedly stable in low-temperature storage. The stability shown is sufficient to permit ' ~ ..
formulations to be shipped and stored without special facilities. It is quite surprising to find that these :
'.
, . .
:. , . : , . , 10498~5 ~
liquid formulations are stable, in view of the known low solubility of metribuzin.
Formulations according to the present invention -have excellent emulsion stability, which is, of course, necessary in order that the formulation can be homogeneously dispersed in water and evenly applied. The emulsion stability has been evaluated by making emulsions of typical formulations in waters of hardness ranging from soft water of 57 ppm. hardness content to very hard water of 1026 ppm.
hardness, and allowing the emulsions to stand at room temperature for 4 hours. The example below shows a typical result.
Example 17 Formulations of this invention were made as follows: -12.6% metribuzin 25.2% trifluralin 10.6% 2-ethoxyethanol 46.6~ xylene 5% Emcol N-300B/N-500B
Formulations were made up in which the ratio of Emcol N-300B and N-500B was varied over a wide range. The emulsion tests were performed by adding 1 ml. of formulation to 100 ml. of water, at room temperature, in a 100 ml.
conical-bottom centrifuge tube. The tube was stoppered and inverted gently a few times to mix the emulsion and was then ; set upright and left undisturbed for 4 hours.
The formulations in which the ratio of emulsifiers was from 4:6 to 2:8 exhibited no instability of the emul-sions in any water over the 4-hour observation period. The ., ,:
10 49~30 5 formulation in which the ratio was 1:9 showed an unmea-surable trace of creaming at the bottom of the observation tube, and the formulation in which the ratio was 5:5 allowed only 0.1 ml. of cream to separate. The formulations in which the ratio of emulsifiers was from 8:2 to 6:4 allowed from no separation to 0.5 ml. of separated cream in the softest water, and allowed only about 0.3 ml. of oil to separate in the hardest water.
Example 18 ~ .
A formulation was made as follows:
- 15.5% metribuzin 23.3% trifluralin 4.0% Emcol N-500B
.. ..
1.0% Emcol N-300B
15.0% 2-ethoxyethanol 41.2% xylene Emulsion stability was tested as described above.
All of the emulsion samples were perfectly stable for 4 ' hours; no separation of the emulsions occurred in any water.
Samples were stored at -5C. for two weeks without precipitation. Precipitation occurred at -19C. after one week of storage; the precipitate redissolved upon warming to -5C.
!
Example 19 The following formulation was prepared:
,, :
16.1% metribuzin ' 21.4% trifluralin 4.0% Emcol N-SOOB -~
1.0% Emcol N-300B
15.0% 2-ethoxyethanol , ' , - - - . - .
.... .. ~
.
': . ' ' ' . '' ~ ' ' ': ' .~ . - . . . . .
42.5% xylene The emulsion sample of this product, also, was stable for 4 hours in all types of water.
; No precipitation of the product occurred in low-temperature storage at -5C. for two weeks. Storage at -19C., however, caused the product to precipitate within a few days.
The manufacture of the formulations is simple.
Only a simple liquid mixing tank, equipped with a low-- 10 powered agitator such as a propeller or a baffled turbine agitator, is necessary. No heating equipment is necessary, although the solvent or the mixture as a whole can be warmed, if desired, to speed the dissolution of the metri-buzin.
The formulations are used according to the normal methods of agricultural chemistry. The proper amount of the formulation to treat an acre of land is emulsified in from about 10 to about 50 gallons of water, depending on the type of application equipment in use, and applied evenly to the soil. Any of the many types of equipment in use for the application of soil-applied agricultural chemicals is perfectly satisfactory for applying the formulations of this ~ ~
invention. ~ --', ~
.
,, , , : ~
., . , . - . ... . .. .. .. . ..
, : .. : : , , :
, . . . . . . .
Claims (4)
1. A stable herbicidal emulsifiable concentrate which comprises from about 10 to about 20 percent of metribuzin;
from about 15 to about 30 percent of trifluralin;
provided that the ratio of the amount of metri-buzin to the amount of trifluralin is from about 1:1 to about 1:2;
from about 3 to about 7 percent of emulsifier comprising a blend of amine salts of alkylarylsulfonates and polyoxyethylene ethers;
from about 8 to about 20 percent of a hydroxylated solvent chosen from the group consisting of 2-ethoxyethanol, 2-methoxyethanol, ethanol and methanol;
and from about 23 to about 64 percent of xylene.
from about 15 to about 30 percent of trifluralin;
provided that the ratio of the amount of metri-buzin to the amount of trifluralin is from about 1:1 to about 1:2;
from about 3 to about 7 percent of emulsifier comprising a blend of amine salts of alkylarylsulfonates and polyoxyethylene ethers;
from about 8 to about 20 percent of a hydroxylated solvent chosen from the group consisting of 2-ethoxyethanol, 2-methoxyethanol, ethanol and methanol;
and from about 23 to about 64 percent of xylene.
2. An emulsifiable concentrate of Claim 1 in which the hydroxylated solvent is 2-ethoxyethanol.
3. An emulsifiable concentrate of Claim 2 in which the ratio of the amount of metribuzin to the amount of trifluralin is about 2:3.
4. The emulsifiable concentrate of Claim 3 which comprises about 15 percent of metribuzin, about 23 percent of trifluralin, about 5 percent of emulsifier, about 15 percent of 2-ethoxyethanol, and about 42 percent of xylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA236,690A CA1049805A (en) | 1975-09-30 | 1975-09-30 | Trifluralin-metribuzin emulsifiable concentrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA236,690A CA1049805A (en) | 1975-09-30 | 1975-09-30 | Trifluralin-metribuzin emulsifiable concentrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049805A true CA1049805A (en) | 1979-03-06 |
Family
ID=4104169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA236,690A Expired CA1049805A (en) | 1975-09-30 | 1975-09-30 | Trifluralin-metribuzin emulsifiable concentrate |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1049805A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206987A1 (en) * | 1985-06-07 | 1986-12-30 | Ciba-Geigy Ag | Herbicidal compositions |
| WO1988004140A1 (en) * | 1986-12-05 | 1988-06-16 | E.I. Du Pont De Nemours And Company | Divalent metal salts improve compositions of asymmetrical triazine mixtures |
-
1975
- 1975-09-30 CA CA236,690A patent/CA1049805A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206987A1 (en) * | 1985-06-07 | 1986-12-30 | Ciba-Geigy Ag | Herbicidal compositions |
| WO1988004140A1 (en) * | 1986-12-05 | 1988-06-16 | E.I. Du Pont De Nemours And Company | Divalent metal salts improve compositions of asymmetrical triazine mixtures |
| US4838927A (en) * | 1986-12-05 | 1989-06-13 | E. I. Du Pont De Nemours And Company | Divalent metal salts improve compositions of asymmetrical triazine mixtures |
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