US2862848A

US2862848A - Emulsifiable insecticide compositions

Info

Publication number: US2862848A
Application number: US535754A
Authority: US
Inventors: Vincent J Keenan
Original assignee: Atlantic Refining Co
Current assignee: Atlantic Richfield Co
Priority date: 1955-09-21
Filing date: 1955-09-21
Publication date: 1958-12-02
Anticipated expiration: 1975-12-02

Description

United States Patent Ofiice 2,862,848 EMULSIFIABLE, INSECTICIDE COMPOSITIONS Vincent J. Keenan, Ardmore',Pa., assignor to The Atlantic Refining Company, Philadelphia, Pa., a corporation of Pennsylvania V H a No Drawing. 1 Application September21, 1955 Serial No. 535,754

12. Claims. (Cl. 167 42) This invention relates to an emulsifiable insecticide composition and, more particularly, to an emulsifiable insecticide composition wherein the insecticide soluble in aromatic hydrocarbons and wherein the emulsifiable agent is a particular ammonium salt of an alkyl aryl sulfonic acid or mixtures of alkyl aryl sulfonic acids, wherein the alkyl group contains 12 carbon atoms or averages 12 carbon atoms, respectively. 7

This application is a continuation-in-part of Vincent J. Keenan application Serial No. 249,807, filed October. 4',

1951, now abandoned, and entitled Emulsifiable Insectisoluble insecticides in water to obtain the necessary dilution.

A number of emulsifying agents have been utilized for this purpose, however, in general, these emulsifying agents have been suitable only for producing emulsions having a rather short time of stability, generally from /2 to 2 hours. Inasmuch as it is desirable when spraying large'orchards or large acreages of crops to make up a batch of emulsion in suflicient quantity .to last for an entire day or, in certain instances, even overnight so that the batch may be utilized in the next days operations, an emulsifying agent is necessary which will produce an emulsion stable for about 24 hours. Furthermore, those emulsions which have only a short time of stability will usually show a tendency to partially break in a very short time with the result that an uneven concentration of insecticide in the spray is produced, thereby over-treating and under-treating various portions of the same field. The emulsions should not be completely stable, however, since if they are completely stable the first rain that comes after application will wash oif the insecticide. In this connection, Dr. A. W. A. Brown in his book Insect Control by Chemicals, John Wiley and Sons, Inc.,*New* 2 York '(1951), at page 55 states: It has been concluded that coarse, quick-breaking emulsions are superior,

since the water quickly runs ofl without taking the oil with it, but instead leaves it as a continuous film. Similarly, Dr. Donald E. H. Frear in his book Chemistry of the Pesticides, D. Van Nostrand Co., Inc. (1955), points out on page 420 that a number of Workers have studied the factors which aflect the deposition of oil from oil emulsion sprays and have shown that as far as the deposit is concerned a quick breaking emulsion is betterthan-one I more stable.

It is an object of this invention to produce an emulsi fiable insecticide composition of an aromatic hydrocarbon soluble insecticide which is stable for about 24 hours.

It is a further object of this invention to produce an emulsifiable insecticide composition of an aromatic hydrocarbon soluble insecticide which has little tendency to partially break during its period of stability.

In accordance with this invention, insecticides such as DDT (2,2-bis(p-chlorophenyl) 1,1,1 trichloroethane),

DDD (2,2-bis (p-chlorophenyl) -1, l-dichloroethane, DFDT I (2,2-bis (p-fluorophenyl) 1,1,1- trichloroethane) DMDT (2,2-bis(p-methylphenyl)-l,l,l trichloroethane), Methoxychlor (2,2-bis (p-methoxyphenyl) 1,l,l-trichlOroethane), Toxaphene (chlorinated camphene; C H Cl Chlo rdane (not less than 60% of l,2,4,5,6,7,8,8-octachlo- 'ro-4,7-methano-3a,4,7,7a-tetrahydroindane, with the re- It has therefore been 7 found necessary to emulsify these aromatic hydrocarbon mainder being related dicyclopentadiene derivatives);

Heptachlor (C H Cl Benzene Hexachloride (hexachlorocyclohexane) Aldrin (1,2,3,4,10,10-hexachloro-1:4, 5 S-diendomethano-l,4,4a,5,8,8a hexahydronaphthalene),

quently sulfonated to produce the desired sulfonic acids 7 may be prepared by a variety of methods, for example, bythe alkylation of an aromatic hydrocarbon with a branch chain olefin having preferably 12 carbon atoms in the presence of a catalyst, such as AlC1 HF, H BF or similar acid type catalysts. The olefin may be obtained from the polymerization of propylene over phosphoric acid or similar catalysts, by the polymerization of butylenes, etc. However, since the polymerization reaction produces a mixture of compounds including those having molecular weights both in excess of and less than those desired, such mixtures must be separated to obtain only those polymers which fall within the C to C range. total product in order to obtain a mixture of olefins wherein the average molecular weight is in the C range and only very small amounts of olefins are present out-1 side the C to C range. The aromatic employed may be benzene, toluene, or any one of the isomeric xylenes or mixtures of such isomers, ethyl benzene, propyl-benzene, and similar lower alkyl aromatics.-

l' 'a t ented Dec. 2, 1958 In other words, a heart cut is taken from the A third method of preparationiofthe alkyl aromatics employs a chlorinated hydrocarbon having 11 to 13 carbon atoms reacted with the aromatic hydrocarbon in the presence of a Friedel-Crafts catalyst such as A101 The alkyl halide may be conveniently obtained by chlorinating the proper petroleum fraction, such as a kerosine fraction. The aromatics suitable in the previous examples are likewise suitable in this method.

Specific examples of the alkyl aromatic hydrocarbons herein contemplated as suitable for the invention are undecyl benzene, undecyl toluene, undecyl ethyl benzene, undecyl dimethyl benzene, undecyl diethyl benzene, undecyl methyl ethyl benzene, undecyl methyl propyl benzene, undecyl dipropyl benzene, dodecyl benzene, dodecyl toluene, dodecyl ethyl benzene, dodecyl propyl benzene, dodecyl dimethyl benzene, dodecyl diethyl benzene, dodecyl methyl ethyl benzene, dodecyl methyl propyl benzene, dodecyl dipropyl benzene, tridecyl benzene, tridecyl toluene, tridecyl ethyl benzene, tridecyl propyl benzene, tridecyl dimethyl benzene, tridecyl diethyl benzene, tridecyl methyl ethyl benzene, tridecyl methyl propyl benzene, tridecyl dipropyl benzene. The above named alkyl aromatic hydrocarbons or mixtures thereof may be sulfonated according to conventional methods, utilizing concentrated (98%) sulfuric acid or fuming sulfuric acid. a

The foregoing methods of preparing the desired sulfonic acids are described in detail in United States Patent No. 2,615,847 and in the references enumerated therein.

The sulfonic acids thus produced may be neutralized by any one of the following organic amines or organic quaternary ammonium compounds: morpholine, pyridine, picoline, trialkanol amines, wherein the alkanol group may contain from 2 to 4 carbon atoms, dialkyl alkanol amines wherein the alkyl groups and alkanol group may contain from 2 to 4 carbon atoms, and tetra alkyl ammonium hydroxide wherein the alkyl groups may contain from 2 to 4 carbon atoms.

It will be apparent from the tables of data which follow that only the above specific ammonium salts of the specific sulfonic acids set forth are suitable as emulsifying agents for the various aromatic hydrocarbon soluble insecticides of the type also enumerated above.

The following examples are presented in order to illustrate specific aspects of the present invention; these examples, however, should not be construed as limiting the invention thereto.

A gas stream comprising about 80 percent propylene with minor amounts of propane, ethane, ethylene and methane was contacted with a catalyst consisting of phosphoric acid impregnated on kieselguhr at a temperature of 500 F. to 550 F. and 400 p. s. i. pressure, at a rate of about 0.1 pound mols of propylene per pound of catalyst per hour. The resulting mixture of propylene polymers containing from 6 to 18 carbon atoms and boiling between 300 F. and about 520 F. was fractionally distilled to remove an overhead fraction boiling between approximately 300 F. and 340 to 360 F. comprising mainly the trimers, i. e. polymers containing 9 carbon 4 atoms, a second cut boiling up to approximately 465 F. and comprising predominantly tetramers (C polymers), leaving a distillation residue or bottoms boiling up to about 520 F. comprising the pentamers or C polymers. Each of these fractions was admixed separately with about 6 molar equivalents of benzene and each mixture treated with an aluminum chloride catalyst at about 140 F. to 150 F. to effect alkylation of the benzene with the propylene polymers. The spent catalyst was separated by settling and the crude alkylate was neutralized with caustic soda solution and then washed with water. The washed crude alkylate was then fractionally distilled to remove excess benzene and alkyl benzenes boiling outside of the desired ranges. In the case of the alkylate produced from the C polymer fraction the monoalkyl benzenes boiling between about 400 F. and 500 F. were separated. In the case of C monoalkyl benzenes a fraction boiling between about 500 F. and 630 F. was separated and in the case of the C monoalkylated benzene a fraction boiling between about 550 F. and 680 F. was separated. In each'case one volume of the alkylated benzene hydrocarbon was contacted with one volume of 98 percent concentration sulfuric acid at about 150 F. for about 30 minutes to produce the monosulfonic acid. The sulfonation reaction mixture was then diluted with about 6 volumes of benzene and permitted to settle and stratify into an upper layer comprising benzene containing the hydrocarbon sulfonic acids with only minor amounts of unsulfonatedhydrocarbons and entrained sul- ;fonic acid. 1 This was then separated from the lower layer containing the spent sulfonic acid.

Seven volumes of the benzene solution of the sulfonic acids was mixed with 4 volumes of 50 percent aqueous methanol. The mixture was stirred and permitted to set- "tle for about ten minutes.

- desired organic amine of organic quaternary ammonium compound of the types mentioned hereinbefore were added. The amount added was sufficient to raise the pH of the solution to 7. This solution was then evaporated to a solids content ranging between 40 to 50 percent by weight. To one volume of the evaporated solution was added 15 volumes of Xylene and the mixture distilled to azeotrope off the water and small amounts of alcohol and benzene thus producing a xylene solution of the sulfonate.

The C C and C alkyl benzene sulfonic acids prepared as described above were separately neutralized with triethanol amine by the foregoing procedure. These salts were used as emulsifying agents and compared with each other and with the triethanol amine salt of a C (lauryl) alcohol sulfate. The results of these experiments are set forth in Table I wherein it will be seen that concentrated solutions of DDT, emulsifying agent, and xylene were prepared and thereafter emulsified with Water in the proportions shown and observations taken after 30 minutes and after 24 hours with regard to the stability of the emulsion.

It is to be noted in the tables of data which follow that the concentration to which the sulfonate solution is reduced by evaporation or other means is not critical since the concentration of sulfonate in the mixture is expressed as percent by Weight of the active sulfonate compound.

ass s is Triethanol ammonium salts as emulsifying agents Emulsion: 1 Vol. of Concentrate Emulsion: 1 Vol. of Conontrate f I and 1 Vol. of Hard Water and 2 Vols. of Hard Water Concentrates Composition (Percentage byWeight) Condition After Conditiom "Condition After. Condition 30 Minutes After 30 Minutes After 24 Hours 24 Hours Partially Stable Partnu some...

65% Xylene (in (Tn' Broken do Broken Stable Sfiah'l Stable 30% DDT 3% 012" Alkyl Benzene Sulfnnate do 67% Xylene 30% DDT 3% On Alkyl Benzene Sulfrmato do do 9. 67% Xylene 3% DDT 2 012" Alkyl Benzene Sulfonetedo do l i V 68% Xylene :i u' z 5 :5. i DDT 1% C1 Alkyl Benzene Sulfonate- Partially Stable Broken.' Broken; 69% Xylene 30% DDT "'1" '1 h. 5% 09" Alkyl Benzene Sulfflflata }Stable Siam The table shows that only the C alkyl benzene "ities when'va rious organic compounds (selected as being fonate emulsions were stable at the end of 24 hours.

In Table H there is presented the results of similar experiments which were conducted to compare a C alkyl benzene sulfonic acid neutralized with caustic (so.- dium hydroxide) and the C alkyl benzene sulfonic acid neutralized with triethauol amine.

The C alkyl benzene sulfonic acid was prepared as described in the example for Table I. One portion was neutralized with triethanol amine as described forthat example of Table I. A second portion of the C alkyl benzene sulfonic acid solution in the aqueous methanol was neutralized to a pH of about7 with a 25% .con-

representative of a large group of compounds tried) were..utilized.-as neutralization agents" for. the sulfonic acid to demonstrate the specificity of theparticular com-, 7

pounds hereinbefore enumerated as being suitable.

' Inea'ch' case'the' C alkyl b enzene sulfonic acid was prepared as described in the example preceding Table I 'Nand neutralized. accordinglfttilthe' lte'jchniques described centration aqueous "sodiumhydroxide solution. This solution about and percen weight;

TABLEII I of Concentrate and 1 Concentrates Composition {Percentage by Weight). 3 ;1: 1,. Condition- V V Condition LY 1 After 30. Aiter24 ml 1 Min ts 11 30% DD Partially.

5% Triethanol -Ammon1um Cm" Alkyl Benzene Sulfonate: i t.

/ Yol. of Hard Waten v as then'evaporat'ed to a solids c'ontent ranging ly ineiiective as an emulsifying agent for,these.-insecticides. 7 Similarly, other inorganic neutralization. agents werefoundto be inefiective.;

In Table III the results are given for emul on stabil in connection with such example:

Table I11 Compositionbf concentrates .30%(W t.) DDT- a 1.5% (wt.) emulsifying agent. I

68.5% (wt;) xylene. u 1 v One volume of eoncentrate added to one volume of hard water and emulsified.

CompoundUsed to Neutralize the Ou'Alkyl Condition Condition Benzene Sulfon io Acid to Prepare the Emulof Emulsion of Emulsion sifying Agent After 30 After 24 .Minutes Hours.-

AmmoniumHydroidde- 'i-- Broken. TetraethylAmmonium Hydroxide Stable. Isopropylamine; Broken. emember- 2, Amino; 1, Birtanol. Do.

MonoethanolAmine o Do. ButylDietlian'ol A'min Brokenm; Do. Trimethyl'Aminese. Stable... Partially Broken Morpholine Diethyl Ethanol Amine .do Arnyl Diethanol Amine Broken Broken 3 Isopropoxy Propyl Aminel. o Do.

This table shows that the sodlum sulfonate 1s entire. s i i V In Table IV a comparison is made of the emulsification tprjopperties of. various, mixtures'of trieth'anol ammoniuni alkyl}benzenelsultonateswith the sodium soap of alien soluble petroleum sulfonic acid extracted from the product obtained by the acid treatment of medicinal white oils.

TABLE-Iv? 8 A concentrate was prepared'by combining a 2.9 percent by wei'ghtjofthe triethanolamine ol'eate, 0.1 percent Blends f triethanol ammonium C alkyl benzene-sulfonate and sodium salts of ptroleum whitelfioil sulfonicf acids Emulsion: 1 Volume of Emulsion: 1 Volume of Concentrate and 1 Concentrate and 2 Volume of Hard Water Volumesot Hard Water Concentrates Composition Condition Atter Condition Afterso Mine. 24 Hrs. 30 Mins. 24 Hrs. I

30% DDT 5% {75% C Sulfonate Stable. Stable... Stable..." Stable.

% Sodium Sultonate...

s% {75% dii'siz'ffiiifiik do (in do Do,

25% Sodium Sultanate...

67g, lgllsl efne 1% 75% 0,, Snlfnnata dn do Brokenm. Broken.

25% Sodium Sulfonate.-.

5 {5 o Silltnnatp do do Stable Partially Sodium S111t'onate. r 7 Stable.

3% {50% Cu Su1tonate do Brokenm- BrokenL... Broken.

50% Sodium Sultana I% {5O% CiiSii ltonat Br do Do.

50% Sodium Sulfonetm;

3 25% drain-rm..- do n m. Do.

75% Sodium Sultonote 1% 25 drain-nan; Beam an do. Do, 75% Sodium Sultonate 69% Xylene This table shows that the petroleum sulfonate by itself is entirely unsuitable as an emulsifying ,agent. Furthermore, these results also show that the alkyl benzene sulfonate cannot be mixed with more than 25 percent of the petroleum sultonate without seriously decreasing the stability of the emulsion. V

A concentrate was produced by combining 2.2 percent by weight of the triethanolamine salt of the C alkyl benzene sul'fonic .acid, 0.4 percent by weight of a petroleum white oil, 0.4 percent by weight of the sodium salt of 7 xylene, and 30 percent by weight DDT. This concentrate was then mixed with water in a ratio of 1 part by weight of concentrate to 5 parts by weight of water to produce an emulsion. V The emulsion broke completely in 10 minutes, showing that oleic acid cannot be substituted for the C alkyl benzene. sulfonic acid to produce tri ethanolarninesalts which will give stable emulsions.

by weight white oil, .67 percent by weight xylene, and 30 percent by weight DDT. This concentrate was then mixed with water in .a ratio of, I part by weight of concentrate to 5 parts by weight of water to produce an emulsion. This emulsion broke within 10 minutes, thus showing that the addition of White oil to the triethanolamine oleate does not give a stable -emulsion.

A concentrate was prepared by combining 3 percent by weight of the triethanolamine salt of a white oil sulfonate, 67 percent by weight xylene, and 30 percent by weight DDT. This concentrate was then mixed with water in a ratio of 1 part by weight of concentrate to 5 parts by weight of water to produce an emulsion. This emulsion broke within 30 minutes, thus demonstrating that neither the triethanol'amine salt nor the sodium salt (Table IV) of white oil sulfonic acids are suitable for stable emulsions.

The above data have all been directed to the emulsification of the particular insecticide DDT, purely for purposes of comparison of the various emulsification agents. In Table V which follows, data are presented on other insecticides demonstrating the applicability of the preferred emulsifying agents to other aromatic hydrocarbon soluble insecticides. Inthese experiments the concentrate was diluted with sufficient water to give the various percentages of insecticide 'in'the emulsion as noted. In each experiment the triethanol ammonium C 5 alkyl benzene-sulfo- 9 V nate of the example of Table I was used as the emulsifying agent.

vent selected from the TABLE v 15% Emulsion 12.5% Emulsion 10% Emulsion 5% Emulsion Concentrates a Composition (Percentage by nd. Atter- 00nd. After- Cond. Mter- Cond. After- Weight) 30 Mine. 24 Hrs. 30 Mins. 24 Hrs. 30 Mins. 24 Hrs. 30 Mine. 24 Hrs.

30% Toxaphene Stable S l Stable... Stable.-. Stable.-. Stable.

} do do do do do 7 Do u do do do do do Do,

do do Brokem. Broken- Broken.

Partially Stable.

Stable... Stable Stable... Stable.

do do do Do.

Partially do do do 72% Xylene Stable. 62% Chlordane f z gfi gf f f Stable... Stable".-. 18% Kerosina- 62%EChlodanie in. gen 6% Xylene- 23% Kerosine 62% Chlordane Em. Agent Partially Br k n 3 3% Xylene Stable. 29.7% Kerosine The insecticides of this invention in addition to being aromatic hydrocarbon soluble may also be characterized as being halogen containing compounds. The various naturally occurring vegetable insecticides such as nicotine, pyrethrins, rotenone, and like compunds, are not included within the scope of this invention since such compounds are generally insoluble in aromatic hydrocarbons and are applied as dusts, or as in the case of nicotine in true water solutions.

In preparing the emulsifiable insecticide composition of this invention, the insecticide is first dissolved in the proper amount of aromatic hydrocarbon, such as xylene or methyl-naphthalene. The ammonium salt of the C alkyl benzene sulfonates of this invention are produced in aqueous solution which is mixed with xylene and the mixture distilled to produce an overhead azeotropic mixture of xylene and water. the water is removed and a xylene solution of the salt remains and may then be mixed with the Xylene solution of the insecticide to produce the concentrate. Generally, the amount of salt based upon the total weight of concentrate may vary from 0.5 per cent to percent, however, from 1. percent to 5 percent is preferred. The concentration of the insecticide may range from 10 percent to 40 percent, generally, and preferably from percent to percent by weight of the concentrate. Obviously, these percentages may vary due to the solubility of the insecticide and of the ammonium salts and in accordance with the desired concentration of insecticide in the emulsion to be used on the crops.

I claim:

1. A water emulsifiable insecticide composition consisting essentially of from 10 percent to 40 percent by weight of a xylene soluble insecticide, from 50 percent to This is continued until all ofconsisting of morpholinium, pyridinium, picolinium, trialkanol ammonium, dialkyl alkanol ammonium, and tetra-alkyl ammonium, wherein the alkanol and alkyl groups contain from 2 to 4 carbon atoms.

2. The composition according to claim 1 wherein the salt is the morpholiniurn salt.

3. The composition according to claim 1 wherein the salt is the pyridinium salt.

4. The composition according to claim 1 wherein the salt is the triethanol ammonium salt.

5. The composition according to claim 1 wherein the salt is the diethyl ethanol ammonium salt.

6. The composition according to claim 1 wherein the salt is the tetraethyl ammonium salt.

7. A water emulsifiable insecticide composition consisting essentially of from 10 percent to 40 percent by Weight of a xylene soluble insecticide, from 50 percent to 89.5 percent by weight of an aromatic hydrocarbon solvent selected from the group consisting of benzene, toluene, xylene, higher alkylated aromatic hydrocarbons and methyl naphthalene, and from 0.5 percent to 10 percent by weight of a salt of an alkyl benzene monosulfonic acid, wherein the alkyl group contains 12 carbon atoms, said salt being selected from the group consisting of morpholinium, pyridinium, picolinium, trialkanol ammonium, dialkyl alkanol ammonium, and tetra-alkyl ammonium, wherein the alkanol and alkyl groups contain 89.5 percent by weight of an aromatic hydrocarbon solfrom 2 to 4 carbon atoms.

group consisting .of benzene; toluene, xylene, higher alkylated aromatic hydrocarbons 8. The composition according to claim 7 wherein the salt is'themorpholinium salt. I

9. The" composition according to claim 7- wherein the salt is pyridinium salt. 2,447,475 10. The composition according to claim 7 wherein the 5 2552187 salt is triethanol ammonium salt. v y H I p 11. The composition according toc'lair'n 7 Whereimth'e 710 415 salt is diethyl ethanol ammonium salt. I v V 12. The composition according to claim 7 Whereinth salt is tetraethyl ammonium salt. V '10 References Cited in the file of this patent UNITED STATES PATENTS Kaberg Aug. 17, 1 948 QIKosmin May 8, 1951 FOREIGNPATENTS France June 8, 1931

Claims

1. A WATER EMULSIFIABLE INSECTICIDE COMPOSITION CONSISTING ESSENTIALLY OF FROM 10 PERCENT TO 40PERCENT BY WEIGHT OF A XYLENE SOLUBLE INSECTICIDE, FROM 50 PERCENT TO 89.5 PERCENT BY WEIGHT OF AN AROMATIC HYDROCARBON SOLVENT SELECTED FROM THE GROUP CONSISTING OF BENZENE, TOLUENE, XYLENE, HIGHER ALKYLATED AROMATIC HYDROCARBONS AND METHYL NAPHTHALENE, AND FROM 0.5 PERCENT TO 10 PERCENT BY WEIGHT OF A SALT OF A MIXTURE OF ALKYL BENZENE MONOSULFONIC ACIDS WHIEREIN THE SUM OF THE CARBON ATOMS IN THE ALKYL GROUPS ATTACHED TO EACH BENZENE RING RANGES BETWEEN 11 TO 19, EACH BENZENE RING HAVING ONE ALKYL GROUP ATTACHED THERETO RANGING BETWEEN 11 AND 13 CARBON ATOMS IN LENGTH, SAID SALT BEING SELECTED FROM THE GROUP CONSISTING OF MORPHOLINIUM, PYRIDINIM, PICOLINIUM, TRIALKANOL AMMONIUM, DIALKYL ALKANOL AMMONIUM, AND TETRA-ALKYL AMMONIUM, WHEREIN THE ALKANOL AND ALKYL GROUPS CONTAIN FROM 2 TO 4 CARBON ATOMS.