CA1121266A - Emulsifiable concentrates of insecticides for use with fluid fertilizers - Google Patents
Emulsifiable concentrates of insecticides for use with fluid fertilizersInfo
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- CA1121266A CA1121266A CA000346552A CA346552A CA1121266A CA 1121266 A CA1121266 A CA 1121266A CA 000346552 A CA000346552 A CA 000346552A CA 346552 A CA346552 A CA 346552A CA 1121266 A CA1121266 A CA 1121266A
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Abstract
Abstract of the Invention An emulsifiable concentrate of an organophosphorus insecticide, in particular, O-ethyl S-phenyl ethylphos-phonodithioate, particularly for use in combination with liquid fertilizers contains as the solvent one or more of certain polyhydric alkanols or polyglycols, their lower alkyl ethers and ether acetates, and/or dioxane, butyrolactone and tetrahydrofurfuryl alcohol.
Description
~ 2 ~ 6 .
P~-5490C
EMULS~FIAB~E CONCENTRATES OF INSECTICID~S FOR USE WITH
~LUID F~RTILIZERS
B~ckground and Pr or Art ; This application relates to lmproved organo-phosphorus insecticide formulations, in the form of emulsif~able concentrates 7 which are particularly sul,able for use in combination with fluid ~ertilizers. More particularly, ehis invention relates to such formulations containing insecticidal phosphono- and phosphoro- mono and dithioates, and preferably the commercial insec~icide O-ethyl S-phenyl ethylphosphonodithioate, known by t`he generic name fonofos. This compound is described in U.S.
~: patent 2,988,474, of Szabo, et al. and is commercially sold under the registered trademark Dyfonate ~ .
Fluid or liquid fertilizers, namely aqueous `' 15 solutions of fertiliæers, and in particular ~-P or N-P-K fertilizers, have been:sold for quite some time in agricultural application. In more recent years, it has become a practice on some occasions to apply a mixture o~ liquid fertilizer together with a liquid formulation of an insecticide to provide both fertili-zation and insect control in connection with ~he culti-vation of certain crops. Once such application which has been performed is the application of a mixture of .
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P~-5490C
EMULS~FIAB~E CONCENTRATES OF INSECTICID~S FOR USE WITH
~LUID F~RTILIZERS
B~ckground and Pr or Art ; This application relates to lmproved organo-phosphorus insecticide formulations, in the form of emulsif~able concentrates 7 which are particularly sul,able for use in combination with fluid ~ertilizers. More particularly, ehis invention relates to such formulations containing insecticidal phosphono- and phosphoro- mono and dithioates, and preferably the commercial insec~icide O-ethyl S-phenyl ethylphosphonodithioate, known by t`he generic name fonofos. This compound is described in U.S.
~: patent 2,988,474, of Szabo, et al. and is commercially sold under the registered trademark Dyfonate ~ .
Fluid or liquid fertilizers, namely aqueous `' 15 solutions of fertiliæers, and in particular ~-P or N-P-K fertilizers, have been:sold for quite some time in agricultural application. In more recent years, it has become a practice on some occasions to apply a mixture o~ liquid fertilizer together with a liquid formulation of an insecticide to provide both fertili-zation and insect control in connection with ~he culti-vation of certain crops. Once such application which has been performed is the application of a mixture of .
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2 ~ 6 insecticide and liquid ~ertilizer as a ~'starter" or "pop-up" mixture prior to, a~,or very shortly after the planting of seeds In the ground, to provide a small amount of fertilizer to be present at the start of plant growth, together with an insecticide to control insects which attac~ the seeds or the early germinating plant while in the soil. Such combinations of insectlcides and liquid fertilizers are described for example, by Petty, et al.~ "Fertilizer Combinations with Herbi-cides or InsectIcides", in "Fertilizer_Technolo~y and Use Second Edition", R.A. Olson, editor; Lindner, "Agricultural Formulations with Liquid Fertillzers" in "Pesticide Formulations", W. Van Valkenburg, Editor;
and Grimes, "Combinations", ~,~,L~L~}~Z~ s 22, No. 8,32-35 (1967).
- In general, these insecticides are insoluble in andlor immiscible with, liquid fertilizers. Mixtures o~ the two are therefore generally produced in the form of emulsions, by combining a liquid fertilizer with an emNlsion, or pre~erably, an emulsifiable concentrate, containing the insecticide. However, problems of - compatibility have been known to exist with such mix-tures. For instance, emulsifiers used in liquid in-secticide formulations may be deactivated by strong salt solutions of liquid fertilizers. The salt concen-trat~ons, i.e. N-P-K ratio of such fertilizers, there-~re, are relevant to the formation of stable mixtures.
If there is a physical incompatibility of the components, one may separate from the mixture, producing problems ranging from clogging of e~uipment to a non-uniform and therefore ineffective or possibly detrimental mixture.
It has been kno~n for some time that agita-tion may be necessary to maintain the stability of an emulsion mixture of a liquid fertilizer with a liquid insecticide and that application without agitation, or '` ' z~
and Grimes, "Combinations", ~,~,L~L~}~Z~ s 22, No. 8,32-35 (1967).
- In general, these insecticides are insoluble in andlor immiscible with, liquid fertilizers. Mixtures o~ the two are therefore generally produced in the form of emulsions, by combining a liquid fertilizer with an emNlsion, or pre~erably, an emulsifiable concentrate, containing the insecticide. However, problems of - compatibility have been known to exist with such mix-tures. For instance, emulsifiers used in liquid in-secticide formulations may be deactivated by strong salt solutions of liquid fertilizers. The salt concen-trat~ons, i.e. N-P-K ratio of such fertilizers, there-~re, are relevant to the formation of stable mixtures.
If there is a physical incompatibility of the components, one may separate from the mixture, producing problems ranging from clogging of e~uipment to a non-uniform and therefore ineffective or possibly detrimental mixture.
It has been kno~n for some time that agita-tion may be necessary to maintain the stability of an emulsion mixture of a liquid fertilizer with a liquid insecticide and that application without agitation, or '` ' z~
-3 storage under non-agitating conditions,can lead to the separa~ion of such mixtures, For th~s reason it ls generally perferable to prepare the mixture just prior to its application ` 5 Fonofos itself is sold in several physical forms includlng an emulsifiable concentrate known as Dyfonate~ 4-EC, ~he "4" lndicatlng the concentration of 4 pounds fonofos per gallon of liquid. This formu-lation contains a petroleum or hydrocarbon solvent and an emulsifier, and has been sold for, among other applications, use as a mixture with liquid or fluid fertiliæers at the time of plant~ng seed corn as a ; start-up mixture in which the insecticide is used to control the corn rootworm. Liquid formulations of fonofos and other organophosphorus insecticides may contain other inert ingredients for special situations, such as corrosion inhibitors. Before actually apply-ing such a mixture, however, it is recommended to prepare a test mixture of fertilizer to be used and fonofos emulsifiable concentrate to determine compat-ibility. Such compatible mixtures are best applied by the use of sprayers and other equipment which pro-vide continual agitation of the mixture 50 as to maintain the stability of the emulsion. In such cases, providing the mixture has not been allowed to stand before being applied, separation of the components does not usually occur. However, it is becoming an increasing practice to provide such starter or pop-up mixtures by the use of a drip method in which the liquid mixture is applied to the soil by ~ripping from a non- -agitated tank or tanks carried on trac~ors or other farm equipment. Preferably, two rows of the mixture are applied per row of corn, one on each side o~ the row of seeds, either during the seed planting or shortly thereafter. Such application may col~sume a period of several hours in order to complete treatment ., ~
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-4-of a field and, in such a situation in which agitation ~s not provided, separation of the fertilizer-insecti-cide mlxture may occur to some extent, re~ulting in the problems mentioned above.
Summary of the Invention According to the present invention there is provided a liquid com~o~ition of an emulsifiable con-centrate of an organophosphorus insecticide, preferably of a member of the group selected from phosphono- and phosphoro- mono and dithioates, and particularly 0-ethyl - lO S-phenyl ethylphosphonodithioate, in which there is employed as the solvent, rather than a petroleum or hydro-carbon ~olvent, a polyalkylene glycol; a polyalkylene glycol mono-lower alkyl ether; an ethylene or propylene glycol mono-lower alkyl e~her; an ethylene glycol mono lower alkyl ether acetate; dioxane; butyrolactone;
tetrahydrofurfuryl alcohol; or a mixture of two or more of these.
In addition, there is provided a liquid com- ~`
position containing an N-P or N-P-K fertilizer and an organophosphorus insectic~de, produced by mix~ng a liquid fertilizer, that is, an aqueous solution of an N-P or N-P-K fertilizer, with an emulsifiable concentrate as -described above.
The polyalkylene glycols used a~ solvents are those generally described by the formula HO(RO)nH, ~n which R is -(CH2)2-, -(CH2)3-, or -~CH2~HCH3~ and ;
n ls a number from 2 to 5. Included in this class are ~;
polyethylene and polypropylene glycols such as di-, tri- and tetra-ethylene glycol, dipropylene glycol, etc.
Also included are mix~ures of such polye~hylene~ glycols;
one such mix~ure is sold by ~nion Carbide Corp. under the trademark "Carbowax 200" and contains a mixture of polyethylene glycols having an average molecular ~e~ght of 190-210. 0~ these, diethylene and triethylene glycols ,., - ~21Z~i~
are part~cularly preferred, and mos~ preferably as co-solvents with mono- or polyglycol ethers, as descr~bed below. Diethylene and dipropylene glycols have been previously used as ~tabilizing agen~s for granular support~
for fonofos and other insectic~des. However, they have ; not been heretofore used in liquid formulations (including emulsifiable concentrates) of such substances, which ` have heretofore incorporated petroleum based or hydro-carbon solvents such as ar~matic naphthas or xylenlc solvents.
The term t'lower alkyl" as used herein in con-` nection with ethers of mono- and polyglycols includes such moieties having from 1 to 4 carbon atoms, particularly methyl, ethyl and n-butyl. Among these, the monomethyl lS ethers appear to provide the best overall performance.
Examples o~ suitable glycol ethers for these compositions are: ethylene glycol monomethyl, monoethyl and mono n-butyl ethers; diethylene glycol monomethyl and mono-n-butyl ethers; triethylene glycol monomethyl ether (methoxy-triglycol); the monomethyl ethers of 1,2-propanediol (propylene glycol) and of its dimer; and tripropylene glycol monomethyl ether.
Examples of suitable glycol ether acetates are ethylene glycol monomethyl, monoethyl and mono-n-butyl ~5 ether acetates.
In preparing liquid emulsifiable concentrates, mixtures of two or more of the above listed solvents may be utilized. Diethylene glycol, in particular, is not miscible wqth fonofos. Therefore, if this solvent is used, it is necessary to utilize~it in the form of a mixture with ano~her solvent, such as triethylene glycol, ethylene glycol monoethyl ether, diethylene glycol mono-methyl ether, etc.
In general, m~tures of two solvents may contain these substances in weight ratio~ of from about -1:1 to about 4:1, with 1:1 mixtures being preferred.
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- : ': '," ~''.`' : :' ~: ' , ` ' ' ~"'~ i z66 The mixtures may contain solvents of ~he same general type te.g. two or more polyalkylene glycols) or o~ different types. Preferred general types of mixtures are mixture~
of different polyethylene glycols and mixtures of poly-ethylene and polypropylene glycols with mono(lower alkyl) ethers of ethylene glycols or of polyethylene- or poly-propylene glycols. Example 8 of suitable mixtures are:
diethylene glycol/triethylene glycol, diethylen~ glycol/
ethylene glycol monoethyl ether, diethylene glycol/
diethylene glycol monomethyl ether, diethylene glycol/
ethylene glycol mono-n-butyl ether, triethylene glycol/
ethylene glycol monoe~hyl ether, triethylene glycol/
diethylene glycol mono-n-butyl ether, tetraethylene glycol/diethylene glycol monomethyl ether, dipropylene glycol/1,2-propanediol monomethyl e~her, dipropylene glycol/ethylene glycol monomethyl ether, 1,2-propanediol monomethyl ether/ethylene glycol monomethyl ether, butyro~
lactane/dioxane, butyrolactone/diethylene glycol, butyrolactone/ethylene glycol monomethyl ether and butyrolactone/diethylene glycol monomethyl ether.
Most preferred of the solvents are the mono-methyl ethers of ethylene glycol and of diethylene glycoL and mixtures of these ethers with diethylene glycol.
Emulsion Stability Tests:
Emulsions containing an insecticide, a solvent, an emulsifier and a liquid fertilixer were subjected to emulsion stability tests utilizing ~he following proce-dure.
A 100 milliliter graduated cylinder was used in all tests. In the cylinder was placed 97.S milli- ;liters of a liquid ~ertilizer. There was then added 2.5 m~lliliters of an emulsifiable concen~rate of an insecticide formulated as indicated. The cylinder was sub~ected to 10 mild inversions of 180 each, at t'ne ambient temperature of the laboratory, (about ?F- or c . .
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~ Z ~6 ; 21C.) and was then left undisturbed for a period of from 1 to 4 hours. The emulsion was visually examined at intervals of 1, 2 and 4 hours, and the mllliliters of cream and oil formed were no~ed. The term "cream" reers to a region of an emulsion ~hich contains a higher propor-tion of the dispersed phase than the average amount ln the system. It is still an emulsion, but its formation indicates a partial separation of components of the emulsified composition. The formation of an oil or appear-ance of clear liquid fertilizer indicates that the emulsion itself is sep æ ating into discrete phases or components.
To show ~he improved results obtained from utilizing compositions of the present invention a number of compara-` tive tests were per~ormed using the experimental procedure described above and different formulations of fonofos and other organophosphorus insecticides. The results of these tests are shown in the following Tables 1-3.
Comparison I
Four differen~ formulations of fonofos emulsifiable concentrates were prepared:
(A) An emulsifiable concentrate containing 49% by weight fonofos, 41% by weight of a xylenic solvent (petroleum-derived fraction containing about 35% xylenes and 60% Cg aroma-tics and heavier) and 10% by weight of a phospha~e ester emulsifying agent.
(B) The same composition as composition (A~
except that the xylenic solvent was replaced by a mixture of 20% by weight diethylene glycol `
monomethyl ether and 21% by weight diethylene glycol.
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~8- ~2~2~6 (C) An emulsifiable liquid containing 47% by weight ~ono~os, 45~0 by welg~ o a heavy aroma-tic naphtha and 8% by weight of a phosphate ester-anionic emulsifying agen~ blend.
(D~ The same as composition (C) with the heavy aromatic naphtha being replaced by mixture o~
20% by weight diethylene glycol monomethyl ether and 25% by weight diethylene glycol. ;
.~ These four compositions were mixed with slx different liquid fertilizer formulat~ons as listed be-low in Table 1 and observed for separation into cream and/or oil phases af~er 1, 2 and 4 hours respectively.
The result of these experiments are given in Table 1 with the figures indicating the number of milliliters observed of cream and oil, respectively, if any. The symbol "t" indica~es the formation of a trace of the particular phase in question. ' ' ~.
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g TAB
Liquid Time, Comp. Comp. Comp. Comp.
Fertilizer hrs. A B C D
10-34-0 1 ~.S/1.5 0/0.5 t/2 0/t 2 1/2 0/1 t/~ 0 . 5/0 . 5 4 2/2 (:~/1 0 . 5/2 1/1 8-24-6 1 0.5/1.5 0 t/l 0 0.5/2 0/t 1/1 0/t 4 0.5/2 0/1 1/1 0/0-5 16-16-4 ~ O O t/2 . 5 2 0 0 'c/2.5 0 4 t/0 0 t/2 . 5 0 7-21-7 1 ~/2 t/~ 1/1 0/1 2 2/2 * 1.5/1 0/1 4 2.5/2 * 2/1 0/1 2 5/0 0/Jc 2.5/0 0 4 4/0 t/t 3/0 0 :
.
3-g-12 1 0 0 1/1 . 5 0/t 2 0 0 1/1.5 0/~
4 0.5/t 0 0.5/2 0/1 10 ml. flocculation obserYed , : ' ' .
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Z~%~66 Comparisons of the results obtained between compositions (A) and (B) and composi~ion~ (C) and (D) respectively show the improved resul~s in maintaining emulsion stability by the use of the formulations con-taining the preferred glycol ether/glycol solvent over the prior art formulations utilizing petroleum-based solvents.
Comparison II
: Similar comparative tests were conducted using the same prooedure, with three additional c~-- 10 positions a`s follows: ~.
(E) An emulsifiable liquid concentrate contain-ing 50% by weight fonofos, 42% by weig~t of the xylenic solvent used in composition (A) and 8%
by weight of an emulsifier which was a blend of ethoxylated phosphate mono- and diesters.
~F) An emulsifiable liquid concentrste contain-ing 47% by weight fonofos, 20~ by weigh~ die~hylene glycol monomethyl ether, 25% by weight diethylene glycol and 8% by weight of the emulsifier used in composition (E).
, (G) The same as composition (F) except that the solvent utilized was ethylene glycol mono- :
methyl ether, which was present in 45% by weight ` of the composition.
The results of the tests of these compositions are shown in the following Table 2 ': : ' ' ~ ' ! ' .
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2~6 TABLE II
Liquid Time, Comp. Contp. Gomp.
F~rtili~erhr. E _ F G
10-34 -0 ~ 2 /0 0 0 4 1~/0 0/t 0/t 8 -~ - 6 1 0 ~ 0 4 0.~/0.5 t/t 0 16-~6-4 1 1/0 0/t 0 2 ~/t 0/t 0 4 2/t 0/'c O
2 1.5/1: t/0 0.5/0 4 1.5/0.5 0.5/0 ~/0 19-19-0 1 2 /~) 0/~ 0/1 2 3/t tl0.5 0/1 4 2/1 t/l 0/1 3-9-12 1 2/0 0.5/0 - 2 2/t l/t 2/t 0.5/0-5 ,- ': ' ,' . ., . ;, ,~ ,;, ' , .. . i . . . .. : . ...... . .. -.. . . : ., ~ . .. , . , :: . .~ ..... .- '1, , .:.
. . . . . . ..
Comparison of the results obtained with compositions (F) and (G) ~ith those of the prior art composition (E) again show the improved results in stability of the emul~ions containing ~he novel com-positions over periods of time up to four hou~.
Comparison III
Using ~he sam~ procedure as in comparisons I and II, tests were performed to determine the stability of emulsions employing the solvents relating to this invention. Different fertilizers were used -liquid formulations of 10-34-0 (N-P) and 7-21-7 and 8-24-6 (N-P-K) fertili~ers. The emulsifiable concen-trates all contained 8 weight % of the emulsifylng agent used in compositions (E), (F) and (G) and had the following compositions (by weight) (H) 47 . 5% fonofos, 44 . 5% dipropylene glycol (DPG);
(I) 46% fonofos, 23% triethylene glycol (TEG), 23% diethylene glycol (DEG);
(J) 50% fonofos, 4270 dioxane (diox);
(K) 50Z fonofos, 42% butyrolactone (Blo);
(L~ 50% fonofos, 21% 1,~fipropanediol mono- ~
methyl e~her ("Propasol ~ , Union Carbide Corp.), :
21% ethylene glycol monomethyl ether (EG-M);
(M) 46% fo~ofos,46% te~rahydrofurfuryl alcohol (THFA);
(N) 46% fonofo~9 23% butyrolactone, 2370 dioxane;
, . . , . , . ~ , , , ..... .. ~ . . ......... ... .
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(0~ 47% fonofos~ 45% die~hylene glycol mono-n-butyl ether (DEG-B);
~P) 47% fono~os, 2270 diethylene glycol mono-n-butyl ether, 23% trie~hylene glycol;
(Q) 47% fonofo~,10% diethylene glycol mono-methyl ethyl (DEG~M), 35% diethylene glycol~
(R) 46% fonofos, 23% butyrolactone, 2370 ethylene glycol monomethyl ether;
(S) 46% fonofosy 23% but~rolactone, 23% diethylene glycol mon~methyl ether;
(T) 46% fonofos, 46% ethylene glycol monomethyl ^~
ether acetate (EG-MA).
Results of these tests are shown in Table 3, with the performance of composition (E) given for c~mpari-son.
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Using the same procedure as in comparison~
I-III, tests were performed to determine ~he stability of emulsions con~aini~g o~her organophosphorus insecti-cides and a solvent of ~his invention. Two emulsifiable : 5 concentrates were prepared, of five sueh insecticides, with one concentrate of each pair employing the xylenic solvent (Xyl.) us~d in composition~ (A~ and (E) and the other, ethylene glyeol monomethyl ether (EG-M).
The five insecticides were:
carbopheno~hion S-[(perchlorophenylthio)me~hyl]0,0-diethyl phosphorodithioate diazinon 0,0-diethyl, 0-(2-isopropyl-4-methyl-6-pyrimidinyl)phosphorothioate disulfoton 0,0-diethyl-S[2-(ethylsulfinyl)ethyl~phosphoro-~` 15 d~thioate methyl parathion 0,0-dimethyl,0-(p-nitrophenyl) phosphorothioate terbuphos s E (t-butylthio)methyl]0,0-diethyl phosphoro-dithioate All the emulsifiable concentrates contained 45 weight % of the insecticide, 8% of the emulsifying .
agent used in compositions (E)-~T) ~nd 47 weight % solvent.
Emulsions were prepared using 10-34-0 (N-P~ and 8-24-6 and 6-18-6 (N-P-K) fertilizers. Results o~ these tests are shown in Table 4.
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A~ can be seen from tl~e forego~ng data, ~he emuls~fiable concQn~rates according to this ill~en~ion, and the emulsions prepared with them, can employ any of a number of conventlonal emulsifying ag~nts, including phosphate esters, phosphate ester-anionic blends and blends of ethoxylated phosphate mono- and diesters. Some suitable emulsifying agents include compositions produced by Witco Chemical Corporation under the designation "Spont~' 168, 225, AK-31-11, 2244, 217 and 221. In all the tests whose results are reported here, the ém~lsifiable concen-trates contained insecticides in a concentration of 46-50%
by weight, and correspondingly, a solvent in an amount of 42-46 weight %. These should not be consldered as lim~ting factors on the proportions of theYe components. Composi-tions suitable for use with liquid fertilizers may contain fonofos or other organophosphorus insecticide~ at levels up to about 75 we~ght %, and as low as 15 weight %, or lower. In addi~ on, while the experiments were all con-ducted using 2.5% (by volume) emulsifiable concentrate and 97.5% (by volume) liquid fertilizer, combinations o~
these two components at other ratios ranging from 1% to 5Z emulsifiable concentrate, may be employed.
Emulsions according to ~hls inven~ion may be prepared in any of several ways, depending on the nature of the liquid fertilizer, the emulsifiable concentrate, the insecticide and the equipment to be used. In some cases, it may be satis~actory to m~x the components in customary fashion, for example by pumping l~quid fer-tilizer into a tank or container holding the emulsifiable concen~rate of insecticide. In other cases, ~pecial te~hniques, including in-line mixin~, may be necessary to obtain a well-mixed emulsion.
While the present emulsiiable concentrates are designed for part~cular use in situations involving ~` 35 the absence of continuous ~g~ta~ on, ~hey can, of course, be sub~tituted for concentrates cont~ining hy~rocarbon or petroleum-based solvents for use ~n applica~ons ~n I
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: ' : ' whlch agitat~on ~s providcd. Xn additîon, such emul-s~fiable concentra~es ~ay be useful in c~mbination with other liquld fertiliæers such as those contair.ing nitrogen only, without phosphorus and potassium com-ponents. The emulsifiable concentrates may also be used alone, with diluents such as water to pro~ide only the insecticide (in insecticidal sprays, for instance~ for the usual appllcations for liquid insecticid~s.
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Summary of the Invention According to the present invention there is provided a liquid com~o~ition of an emulsifiable con-centrate of an organophosphorus insecticide, preferably of a member of the group selected from phosphono- and phosphoro- mono and dithioates, and particularly 0-ethyl - lO S-phenyl ethylphosphonodithioate, in which there is employed as the solvent, rather than a petroleum or hydro-carbon ~olvent, a polyalkylene glycol; a polyalkylene glycol mono-lower alkyl ether; an ethylene or propylene glycol mono-lower alkyl e~her; an ethylene glycol mono lower alkyl ether acetate; dioxane; butyrolactone;
tetrahydrofurfuryl alcohol; or a mixture of two or more of these.
In addition, there is provided a liquid com- ~`
position containing an N-P or N-P-K fertilizer and an organophosphorus insectic~de, produced by mix~ng a liquid fertilizer, that is, an aqueous solution of an N-P or N-P-K fertilizer, with an emulsifiable concentrate as -described above.
The polyalkylene glycols used a~ solvents are those generally described by the formula HO(RO)nH, ~n which R is -(CH2)2-, -(CH2)3-, or -~CH2~HCH3~ and ;
n ls a number from 2 to 5. Included in this class are ~;
polyethylene and polypropylene glycols such as di-, tri- and tetra-ethylene glycol, dipropylene glycol, etc.
Also included are mix~ures of such polye~hylene~ glycols;
one such mix~ure is sold by ~nion Carbide Corp. under the trademark "Carbowax 200" and contains a mixture of polyethylene glycols having an average molecular ~e~ght of 190-210. 0~ these, diethylene and triethylene glycols ,., - ~21Z~i~
are part~cularly preferred, and mos~ preferably as co-solvents with mono- or polyglycol ethers, as descr~bed below. Diethylene and dipropylene glycols have been previously used as ~tabilizing agen~s for granular support~
for fonofos and other insectic~des. However, they have ; not been heretofore used in liquid formulations (including emulsifiable concentrates) of such substances, which ` have heretofore incorporated petroleum based or hydro-carbon solvents such as ar~matic naphthas or xylenlc solvents.
The term t'lower alkyl" as used herein in con-` nection with ethers of mono- and polyglycols includes such moieties having from 1 to 4 carbon atoms, particularly methyl, ethyl and n-butyl. Among these, the monomethyl lS ethers appear to provide the best overall performance.
Examples o~ suitable glycol ethers for these compositions are: ethylene glycol monomethyl, monoethyl and mono n-butyl ethers; diethylene glycol monomethyl and mono-n-butyl ethers; triethylene glycol monomethyl ether (methoxy-triglycol); the monomethyl ethers of 1,2-propanediol (propylene glycol) and of its dimer; and tripropylene glycol monomethyl ether.
Examples of suitable glycol ether acetates are ethylene glycol monomethyl, monoethyl and mono-n-butyl ~5 ether acetates.
In preparing liquid emulsifiable concentrates, mixtures of two or more of the above listed solvents may be utilized. Diethylene glycol, in particular, is not miscible wqth fonofos. Therefore, if this solvent is used, it is necessary to utilize~it in the form of a mixture with ano~her solvent, such as triethylene glycol, ethylene glycol monoethyl ether, diethylene glycol mono-methyl ether, etc.
In general, m~tures of two solvents may contain these substances in weight ratio~ of from about -1:1 to about 4:1, with 1:1 mixtures being preferred.
, .
' '`` ~ ' ` ` .' ' ~ ` :
- : ': '," ~''.`' : :' ~: ' , ` ' ' ~"'~ i z66 The mixtures may contain solvents of ~he same general type te.g. two or more polyalkylene glycols) or o~ different types. Preferred general types of mixtures are mixture~
of different polyethylene glycols and mixtures of poly-ethylene and polypropylene glycols with mono(lower alkyl) ethers of ethylene glycols or of polyethylene- or poly-propylene glycols. Example 8 of suitable mixtures are:
diethylene glycol/triethylene glycol, diethylen~ glycol/
ethylene glycol monoethyl ether, diethylene glycol/
diethylene glycol monomethyl ether, diethylene glycol/
ethylene glycol mono-n-butyl ether, triethylene glycol/
ethylene glycol monoe~hyl ether, triethylene glycol/
diethylene glycol mono-n-butyl ether, tetraethylene glycol/diethylene glycol monomethyl ether, dipropylene glycol/1,2-propanediol monomethyl e~her, dipropylene glycol/ethylene glycol monomethyl ether, 1,2-propanediol monomethyl ether/ethylene glycol monomethyl ether, butyro~
lactane/dioxane, butyrolactone/diethylene glycol, butyrolactone/ethylene glycol monomethyl ether and butyrolactone/diethylene glycol monomethyl ether.
Most preferred of the solvents are the mono-methyl ethers of ethylene glycol and of diethylene glycoL and mixtures of these ethers with diethylene glycol.
Emulsion Stability Tests:
Emulsions containing an insecticide, a solvent, an emulsifier and a liquid fertilixer were subjected to emulsion stability tests utilizing ~he following proce-dure.
A 100 milliliter graduated cylinder was used in all tests. In the cylinder was placed 97.S milli- ;liters of a liquid ~ertilizer. There was then added 2.5 m~lliliters of an emulsifiable concen~rate of an insecticide formulated as indicated. The cylinder was sub~ected to 10 mild inversions of 180 each, at t'ne ambient temperature of the laboratory, (about ?F- or c . .
- . ~; , . .... . ........ . ~ .. ;
.. ~ .:, .. . .. . .
: :
~ Z ~6 ; 21C.) and was then left undisturbed for a period of from 1 to 4 hours. The emulsion was visually examined at intervals of 1, 2 and 4 hours, and the mllliliters of cream and oil formed were no~ed. The term "cream" reers to a region of an emulsion ~hich contains a higher propor-tion of the dispersed phase than the average amount ln the system. It is still an emulsion, but its formation indicates a partial separation of components of the emulsified composition. The formation of an oil or appear-ance of clear liquid fertilizer indicates that the emulsion itself is sep æ ating into discrete phases or components.
To show ~he improved results obtained from utilizing compositions of the present invention a number of compara-` tive tests were per~ormed using the experimental procedure described above and different formulations of fonofos and other organophosphorus insecticides. The results of these tests are shown in the following Tables 1-3.
Comparison I
Four differen~ formulations of fonofos emulsifiable concentrates were prepared:
(A) An emulsifiable concentrate containing 49% by weight fonofos, 41% by weight of a xylenic solvent (petroleum-derived fraction containing about 35% xylenes and 60% Cg aroma-tics and heavier) and 10% by weight of a phospha~e ester emulsifying agent.
(B) The same composition as composition (A~
except that the xylenic solvent was replaced by a mixture of 20% by weight diethylene glycol `
monomethyl ether and 21% by weight diethylene glycol.
- - ' :
.
~ . `
~8- ~2~2~6 (C) An emulsifiable liquid containing 47% by weight ~ono~os, 45~0 by welg~ o a heavy aroma-tic naphtha and 8% by weight of a phosphate ester-anionic emulsifying agen~ blend.
(D~ The same as composition (C) with the heavy aromatic naphtha being replaced by mixture o~
20% by weight diethylene glycol monomethyl ether and 25% by weight diethylene glycol. ;
.~ These four compositions were mixed with slx different liquid fertilizer formulat~ons as listed be-low in Table 1 and observed for separation into cream and/or oil phases af~er 1, 2 and 4 hours respectively.
The result of these experiments are given in Table 1 with the figures indicating the number of milliliters observed of cream and oil, respectively, if any. The symbol "t" indica~es the formation of a trace of the particular phase in question. ' ' ~.
'.
g TAB
Liquid Time, Comp. Comp. Comp. Comp.
Fertilizer hrs. A B C D
10-34-0 1 ~.S/1.5 0/0.5 t/2 0/t 2 1/2 0/1 t/~ 0 . 5/0 . 5 4 2/2 (:~/1 0 . 5/2 1/1 8-24-6 1 0.5/1.5 0 t/l 0 0.5/2 0/t 1/1 0/t 4 0.5/2 0/1 1/1 0/0-5 16-16-4 ~ O O t/2 . 5 2 0 0 'c/2.5 0 4 t/0 0 t/2 . 5 0 7-21-7 1 ~/2 t/~ 1/1 0/1 2 2/2 * 1.5/1 0/1 4 2.5/2 * 2/1 0/1 2 5/0 0/Jc 2.5/0 0 4 4/0 t/t 3/0 0 :
.
3-g-12 1 0 0 1/1 . 5 0/t 2 0 0 1/1.5 0/~
4 0.5/t 0 0.5/2 0/1 10 ml. flocculation obserYed , : ' ' .
, ~
Z~%~66 Comparisons of the results obtained between compositions (A) and (B) and composi~ion~ (C) and (D) respectively show the improved resul~s in maintaining emulsion stability by the use of the formulations con-taining the preferred glycol ether/glycol solvent over the prior art formulations utilizing petroleum-based solvents.
Comparison II
: Similar comparative tests were conducted using the same prooedure, with three additional c~-- 10 positions a`s follows: ~.
(E) An emulsifiable liquid concentrate contain-ing 50% by weight fonofos, 42% by weig~t of the xylenic solvent used in composition (A) and 8%
by weight of an emulsifier which was a blend of ethoxylated phosphate mono- and diesters.
~F) An emulsifiable liquid concentrste contain-ing 47% by weight fonofos, 20~ by weigh~ die~hylene glycol monomethyl ether, 25% by weight diethylene glycol and 8% by weight of the emulsifier used in composition (E).
, (G) The same as composition (F) except that the solvent utilized was ethylene glycol mono- :
methyl ether, which was present in 45% by weight ` of the composition.
The results of the tests of these compositions are shown in the following Table 2 ': : ' ' ~ ' ! ' .
'.' . , .' .
. . .
2~6 TABLE II
Liquid Time, Comp. Contp. Gomp.
F~rtili~erhr. E _ F G
10-34 -0 ~ 2 /0 0 0 4 1~/0 0/t 0/t 8 -~ - 6 1 0 ~ 0 4 0.~/0.5 t/t 0 16-~6-4 1 1/0 0/t 0 2 ~/t 0/t 0 4 2/t 0/'c O
2 1.5/1: t/0 0.5/0 4 1.5/0.5 0.5/0 ~/0 19-19-0 1 2 /~) 0/~ 0/1 2 3/t tl0.5 0/1 4 2/1 t/l 0/1 3-9-12 1 2/0 0.5/0 - 2 2/t l/t 2/t 0.5/0-5 ,- ': ' ,' . ., . ;, ,~ ,;, ' , .. . i . . . .. : . ...... . .. -.. . . : ., ~ . .. , . , :: . .~ ..... .- '1, , .:.
. . . . . . ..
Comparison of the results obtained with compositions (F) and (G) ~ith those of the prior art composition (E) again show the improved results in stability of the emul~ions containing ~he novel com-positions over periods of time up to four hou~.
Comparison III
Using ~he sam~ procedure as in comparisons I and II, tests were performed to determine the stability of emulsions employing the solvents relating to this invention. Different fertilizers were used -liquid formulations of 10-34-0 (N-P) and 7-21-7 and 8-24-6 (N-P-K) fertili~ers. The emulsifiable concen-trates all contained 8 weight % of the emulsifylng agent used in compositions (E), (F) and (G) and had the following compositions (by weight) (H) 47 . 5% fonofos, 44 . 5% dipropylene glycol (DPG);
(I) 46% fonofos, 23% triethylene glycol (TEG), 23% diethylene glycol (DEG);
(J) 50% fonofos, 4270 dioxane (diox);
(K) 50Z fonofos, 42% butyrolactone (Blo);
(L~ 50% fonofos, 21% 1,~fipropanediol mono- ~
methyl e~her ("Propasol ~ , Union Carbide Corp.), :
21% ethylene glycol monomethyl ether (EG-M);
(M) 46% fo~ofos,46% te~rahydrofurfuryl alcohol (THFA);
(N) 46% fonofo~9 23% butyrolactone, 2370 dioxane;
, . . , . , . ~ , , , ..... .. ~ . . ......... ... .
, . , , . , - ,.` ~,' "'' '' ,~' .,1 ~ " ' '' .! :
(0~ 47% fonofos~ 45% die~hylene glycol mono-n-butyl ether (DEG-B);
~P) 47% fono~os, 2270 diethylene glycol mono-n-butyl ether, 23% trie~hylene glycol;
(Q) 47% fonofo~,10% diethylene glycol mono-methyl ethyl (DEG~M), 35% diethylene glycol~
(R) 46% fonofos, 23% butyrolactone, 2370 ethylene glycol monomethyl ether;
(S) 46% fonofosy 23% but~rolactone, 23% diethylene glycol mon~methyl ether;
(T) 46% fonofos, 46% ethylene glycol monomethyl ^~
ether acetate (EG-MA).
Results of these tests are shown in Table 3, with the performance of composition (E) given for c~mpari-son.
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Using the same procedure as in comparison~
I-III, tests were performed to determine ~he stability of emulsions con~aini~g o~her organophosphorus insecti-cides and a solvent of ~his invention. Two emulsifiable : 5 concentrates were prepared, of five sueh insecticides, with one concentrate of each pair employing the xylenic solvent (Xyl.) us~d in composition~ (A~ and (E) and the other, ethylene glyeol monomethyl ether (EG-M).
The five insecticides were:
carbopheno~hion S-[(perchlorophenylthio)me~hyl]0,0-diethyl phosphorodithioate diazinon 0,0-diethyl, 0-(2-isopropyl-4-methyl-6-pyrimidinyl)phosphorothioate disulfoton 0,0-diethyl-S[2-(ethylsulfinyl)ethyl~phosphoro-~` 15 d~thioate methyl parathion 0,0-dimethyl,0-(p-nitrophenyl) phosphorothioate terbuphos s E (t-butylthio)methyl]0,0-diethyl phosphoro-dithioate All the emulsifiable concentrates contained 45 weight % of the insecticide, 8% of the emulsifying .
agent used in compositions (E)-~T) ~nd 47 weight % solvent.
Emulsions were prepared using 10-34-0 (N-P~ and 8-24-6 and 6-18-6 (N-P-K) fertilizers. Results o~ these tests are shown in Table 4.
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2~6~
A~ can be seen from tl~e forego~ng data, ~he emuls~fiable concQn~rates according to this ill~en~ion, and the emulsions prepared with them, can employ any of a number of conventlonal emulsifying ag~nts, including phosphate esters, phosphate ester-anionic blends and blends of ethoxylated phosphate mono- and diesters. Some suitable emulsifying agents include compositions produced by Witco Chemical Corporation under the designation "Spont~' 168, 225, AK-31-11, 2244, 217 and 221. In all the tests whose results are reported here, the ém~lsifiable concen-trates contained insecticides in a concentration of 46-50%
by weight, and correspondingly, a solvent in an amount of 42-46 weight %. These should not be consldered as lim~ting factors on the proportions of theYe components. Composi-tions suitable for use with liquid fertilizers may contain fonofos or other organophosphorus insecticide~ at levels up to about 75 we~ght %, and as low as 15 weight %, or lower. In addi~ on, while the experiments were all con-ducted using 2.5% (by volume) emulsifiable concentrate and 97.5% (by volume) liquid fertilizer, combinations o~
these two components at other ratios ranging from 1% to 5Z emulsifiable concentrate, may be employed.
Emulsions according to ~hls inven~ion may be prepared in any of several ways, depending on the nature of the liquid fertilizer, the emulsifiable concentrate, the insecticide and the equipment to be used. In some cases, it may be satis~actory to m~x the components in customary fashion, for example by pumping l~quid fer-tilizer into a tank or container holding the emulsifiable concen~rate of insecticide. In other cases, ~pecial te~hniques, including in-line mixin~, may be necessary to obtain a well-mixed emulsion.
While the present emulsiiable concentrates are designed for part~cular use in situations involving ~` 35 the absence of continuous ~g~ta~ on, ~hey can, of course, be sub~tituted for concentrates cont~ining hy~rocarbon or petroleum-based solvents for use ~n applica~ons ~n I
!
.' . , ' ': : :
,; ,' '' ~ `, ' ` ', ' `' '.' '` '. `
" ' , ' ', '~ ~' ' '' '' '. "
: ' : ' whlch agitat~on ~s providcd. Xn additîon, such emul-s~fiable concentra~es ~ay be useful in c~mbination with other liquld fertiliæers such as those contair.ing nitrogen only, without phosphorus and potassium com-ponents. The emulsifiable concentrates may also be used alone, with diluents such as water to pro~ide only the insecticide (in insecticidal sprays, for instance~ for the usual appllcations for liquid insecticid~s.
: ~ , .
`,:
.
Claims (48)
1. An emulsifiable concentrate composition comprising:
(a) an organophosphorus insecticide; and (b) a solvent selected from the group con-sisting of:
(i) polyalkylene glycols having the for-mula HO(RO)nH in which R is -(CH2)2-, -(CH2)3- or -(CH2CHCH3)-and n is a number from 2 to 5;
(ii) mono-lower alkyl ethers of said poly-alkylene glycols;
(iii) mono-lower alkyl ethers of ethylene glycol and 1, 2-propanediol;
(iv) mono-lower alkyl ether acetates of ethylene glycol;
(v) dioxane;
(vi) butyrolactone;
(vii) tetxahydrofurfuryl alcohol; and (viii) mixtures thereof.
(a) an organophosphorus insecticide; and (b) a solvent selected from the group con-sisting of:
(i) polyalkylene glycols having the for-mula HO(RO)nH in which R is -(CH2)2-, -(CH2)3- or -(CH2CHCH3)-and n is a number from 2 to 5;
(ii) mono-lower alkyl ethers of said poly-alkylene glycols;
(iii) mono-lower alkyl ethers of ethylene glycol and 1, 2-propanediol;
(iv) mono-lower alkyl ether acetates of ethylene glycol;
(v) dioxane;
(vi) butyrolactone;
(vii) tetxahydrofurfuryl alcohol; and (viii) mixtures thereof.
2. A composition according to Claim 1 in which the insecticide is selected from the group consisting of phosphono- and phosphoro- mono- and dithioates.
3. A composition according to Claim 1 in which the insecticide is fonofos.
4. A ccmposition sccording to Claim 1 in which the solvent is selected from types (i), (ii), (iii) and mixtures thereof.
5. A composition according to Claim 1 in which the solvent is a mono(lower alkyl) ether of a polyalkylene glycol.
6. A composition according to Claim 5 in which the solvent is a mono(lower alkyl) ether of diethylene glycol.
7. A composition according to Claim 6 in which the solvent is diethylene glycol monomethyl ether.
8. A composition according to Claim 5 in which the solvent is a mono(lower alkyl) ether of a poly-alkylene glycol having the formula HO[CH2CH(CH3)0]nH
in which n is a number from 2 to 5.
in which n is a number from 2 to 5.
9. A composition according to Claim 5 in which the solvent is a mono(lower alkyl) ether of a poly-alkylene glycol having the formula HO[(CH2)30]nH in which n is a number from 2 to 5.
10. A composition according to Claim 1 in which the solvent is a mono(lower alkyl) ether of ethylene glycol.
ll. A composition according to Claim 10 in which the solvent is ethylene glycol monomethyl either.
12. A composition according to Claim 10 in which the solvent is ethylene glycol monoethyl ether.
13. A composition according to Claim 1 in which the solvent is 1,2-propanediol monomethyl ether.
14. A composition according to Claim 1 in which the solvent is a polyalkylene glycol.
15. A composition according to Claim 14 in whieh the solvent is triethylene glycol.
16. A composition according to Claim 14 in which the solvent is tetraethylene glycol.
17. A composition according to Claim 14 in whlch the solvent is dipropylene glycol.
18. A composition according to Claim 1 in which the solvent is a mixtuxe of po1yalkylene glycols.
19. A composition according to Claim 18 in which the solvent is a mixture of diethylene and triethylene glycols.
20. A composition according to Claim 1 in which the solvent is a mixture of a polyalkylene glycol and a mono(lower alkyl) ether of a polyalkylene glycol.
21. A composition according to Claim 20 in which the solvent is a mixture of diethylene glycol and di-ethylene glycol monomethyl ether.
22. A composition according to Claim 20 in which the solvent is a mixture of triethylene glycol and di-ethylene glycol monomethyl ether.
23. A composition according to Claim 1 in which the solvent is a mixture of a polyalkylene glycol and a mono(lower alkyl) ether of ethylene glycol.
24. A composition according to Claim 23 in which the solvent is a mixture of diethylene glycol and ethylene glycol monoethyl ether.
25. A composition according to Claim 23 in which the solvent is a mixture of dipropylene glycol and ethylene glycol monomethyl ether.
26. A composition according to Claim 23 in which the solvent is a mixture of triethylene glycol and ethylene glycol monoethyl ether.
27. A composition according to Claim 1 in which the solvent is a mixture of dipropylene glycol and 1,2-propanediol monomethyl ether.
28. A composition according to Claim 1 in which the solvent is a mixture of the monomethyl ethers of ethylene glycol and of 1,2 -propanediol.
29. A composition according to Claim 1 in which the solvent is butyrolactone.
30. A composition according to Claim 1 in which the solvent is a mixture of butyrolactone and ethylene glycol monomethyl ether.
31. A composition according to Claim 1 in which the solvent is a mixture of butyrolactone and diethylene glycol monomethyl ether.
32. A composition according to Claim 1 in which the solvent is a mono-lower alkyl ether acetate of ethylene glycol.
33. A composition according to Claim 1 in which the solvent is ethylene glycol monomethyl ether acetate.
34. A composition according to Claim 1 containing between about 15 and about 75% by weight of the insecti-cide.
35. A composition accordlng to Claim 1 in which the solvent is a mixture of two members, in a weight ratio of between about 1:1 and about 4:1.
36. An emulsion composition comprising:
(a) An emulsifiable concentrate as defined in Claim 1, and (b) an aqueous solution of an N-P or N-P-K
fertilizer.
(a) An emulsifiable concentrate as defined in Claim 1, and (b) an aqueous solution of an N-P or N-P-K
fertilizer.
37. A composition according to Claim 36 in which the fertilizer is an N-P fertilizer.
38. A composition according to Claim 37 com-prising 10-34-0 fertilizer.
39. A composition according to Claim 37 com-prising 19-19-0 fertilizer.
40. A composition according to Claim 36 in which the fertilizer is an N-P-K fertilizer.
41. A composition according to Claim 40 com-prising 8-24-6 fertilizer.
42. A composition according to Claim 40 com-prising 16-16-4 fertilizer.
43. A composition according to Claim 40 com-prising 7-21-7 fertilizer.
44. A composition according to Claim 40 com-prising 3-9-12 fertilizer.
45. A composition according to Claim 40 com-prising 6-18-6 fertilizer.
46. A composition according to Claim 36 com-prising 1-5% by weight of the emulsifiable concentrate.
47. A composition according to Claim 36 in which the solvent is ethylene glycol monomethyl ether.
48. A composition according to Claim 36 in which the solvent in a mixture of diethylene glycol and di-ethylene glycol monomethyl ether.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1954879A | 1979-03-12 | 1979-03-12 | |
| US19,548 | 1979-03-12 | ||
| US10712979A | 1979-12-26 | 1979-12-26 | |
| US107,129 | 1979-12-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121266A true CA1121266A (en) | 1982-04-06 |
Family
ID=26692325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000346552A Expired CA1121266A (en) | 1979-03-12 | 1980-02-27 | Emulsifiable concentrates of insecticides for use with fluid fertilizers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1121266A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2518456A (en) * | 2012-10-15 | 2015-03-25 | Gowan Com Internac E Servicos Limitada | A water miscible solvent system for agrochemicals and uses thereof |
-
1980
- 1980-02-27 CA CA000346552A patent/CA1121266A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2518456A (en) * | 2012-10-15 | 2015-03-25 | Gowan Com Internac E Servicos Limitada | A water miscible solvent system for agrochemicals and uses thereof |
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