US3424847A - Toxicant concentrates containing acetonitrile and emulsifiers - Google Patents

Description

United States Patent: 0

3,424,847 TOXICANT CONCENTRAT ES CONTAINING ACETONITRILE AND EMULSIFIERS Edgar Selz, Evanston, Ill., assignor to Witco Chemical Company, Inc., New York, N.Y., a corporation of Delaware No Drawing. Filed Nov. 18, 1963, Ser. No. 324,251 US. Cl. 424-304 7 Claims Int. Cl. AOliu 9/04, 17/10 ABSTRACT OF THE DISCLOSURE Emulsifier compositions, as well as toxicant concentrates containing said emulsifier compositions, comprising essentially clear liquids at room temperature, said emulsifier compositions containing an acetonitrile-soluble and watersoluble to readily water-dispersible nonionic emulsifier of the type which includes in its molecule a hydrophobic group and at least 8 oxyethylene groups, said compositions containing acetonitrile in proportions of from I to 20%, by weight, of the emulsifier composition.

My invention relates to emulsifier compositions and is particularly concerned with emulsifier compositions which comprise water-soluble or readily water-dispersible emulsifiers of the type which contain a number of recurring oxyethylene groups or units and which are conventionally used for the production of emulsifiable toxicant-containing concentrates and toxicant-containing emulsions for use for agricultural and related purposes.

Water-soluble or readily water-dispersible nonionic emulsifiers of the type which contain a number of recurring oxyethylene groups or units have long been known and are in widespread use. They take many forms but, in at least most cases, they are characterized by containing, in their molecules, a total of from 8 to 20 or 30 and not uncommonly up to about 60 or more oxyethylene groups which are linked, in the molecule of the said nonionic emulsifier, directly or indirectly. that is. through other linkages, to a higher molecular weight hydrophobic radical containing from 8 to 26 carbon atoms, said hydrophobic radical commonly being in the form of an alkyl radical or a monocarboxylic acid acyl radical containing from 8 to 26 carbon atoms, particularly from l2 to 16 carbon atoms; or an alkylated aryl radical, notably an alkylated benzene, toluene, phenol or naphthalene radical containing from 12 to 26 carbon atoms, particularly from 15 to 22 carbon atoms. Especially desirable nonionic emulsifiers for use in the practice of my present invention are 15 to 30 mo] ethylene oxide adducts of nonyl phenol or mixtures of ethylene oxide adducts of nonyl phenol with different contents of ethylene oxide, advantageously within the aforesaid areas.

It is also well known in the art to utilize the aforesaid nonionic emulsifiers in conjunction with anionic emulsifiers and to market them as emulsifier compositions dis solved or dispersed in organic solvents or mixtures of organic solvents. Typical of such anionic emulsifiers, of which large classes and large numbers of such classes are well known to the art, are higher molecular weight, gen erally C C alkyl sulfates such as dodecyl sulfate in the form of such salts as the sodium salt and the monoethanolamine, diethanolamine, triethanolamine and isopropanolamine salts; the higher molecular weight, generally C -C alkyl benzene and alkyl naphthalene sulfonates such as dodecyl benzene sulfonate, tridecyl benzene sulfonate, pentadecyl benzene sulfonates and the corresponding alkyl naphthalene sulfonates, in the form of the aforementioned salts as well as the calcium and magnesium salts; sulfopolycarboxylic acid esters of higher molecular weight, generally C -C fatty acid amides of 3,424,847 Patented Jan. 28, 1969 alcohol primary or secondary amines such as sulfosuccinic acid esters of lauric and myristic acid amides of monoethanolamine, dicthanolamine and monoisopropanolamine, in the form of their alkali metal, ammonium. and amine salts such as the isopropylamine salt, and the half alkali metal-half amine salts such as the half ammoniumhalf isopropylamine salt of the sulfosuccinic acid ester of the oleic acid amide of monoisopropanolamine; the sulfates of higher molecular weight (generally C to C fatty acid monoglycerides exemplified by the monos'ulfates of lauric or myristic or coconut oil mixed fatty acid monoesters of glycerine, in the form of their alkali metal. ammonium or amine salts; and phosphoric acid esters of 25 to 35 mol ethylene oxide adducts of nonyl phenol. Especially desirable anionic emulsifiers for use in the practice of my present invention are calcium and lower amine salts of monododecyl benzene monosulfonic acid, examples of the latter being isopropylamine salts and aminoethylethanolamine salts of monododecyl benzene monosulfonic acid.

The aforesaid types of emulsifiers and emulsifier compositions are, as indicated above, commonly marketed as such as well as in the form of toxicant containing concentrates, said concentrates being intended for admixture with water to produce aqueous emulsions or dispersions which are applied to plants, earth soils and like agricultural environments as pesticides or insecticides, soil fumigants, nematocides, herbicides, fungicides, rodenticides, miticides, disinfectants and the like, hereafter, for convenience, designated simply as toxicants.

Emulsifiers and emulsifier compositions of the fore going types especially, and to a somewhat lesser extent toxicant concentrates containing the same, although in widespread commercial use, nevertheless have numbers of objections. Many such emulsifier compositions. for instance, although producing excellent dispersions in aqueous media for application to plants, insects, etc. when used in producing toxicant concentrate formulations, tend, on storage or in shipment and even when freshly prepared, to separate into layers or to thicken. This is particularly the case where said compositions stand over a period of time in storage or during shipment and is aggravated by low temperature conditions. While this does not destroy their ultimate usefulness, it frequently renders difiicult their handling and it also has definite objections from the standpoint of the appearance of the compositions. In an effort to solve these problems, it has been common practice to add varying amounts, for instance from 3 to 20% by weight of the emulsifier compositions, of methanol or denatured ethanol to maintain the compositions in a fluid state. For a variety of reasons, this practice is not entirely satisfactory. Attempts to replace the methanol or denatured ethanol have resulted in additional objections such as excessive quantities of the attempted replacements, for instance. n propanol and isopropanol, being required, and lack of clarity of the emulsifier compositions and toxicant concentrates.

I have discovered that acetonitrile is unusually and uncxpectedly effective as a solvent in emulsifier compositions of the type which I have described above, especially where the nonionic emulsifier of the type referred to above and discussed in further detail below is a solid at room temperatures or below. In the first place. it maintains the emulsifier compositions in a fluid or mobile state over prolonged periods of time. In addition, it imparts much greater clarity to the emulsifier compositions than even the methanol and the denatured ethanol. Finally, in various emulsifier compositions. its use eliminates or sharply reduces layer separations. it is especially efficacious in emulsifier compositions and toxicant concentrates containing the same where the nonionic emulsifie em ployed is or includes one or more which is a solid at or below room temperatures. The acetonitrile may be used as the sole organic liquid in which the nonionic emulsifier, or nonionic emulsifier and anionic emulsifier, are dissolved. In such case, high emulsifier concentrations can be made which still retain good mobility or liquidity even at relatively low temperatures. It is, however, especially desirable that the acetonitrile be employed in conjunction with one or more organic solvents, particularly hydrocarbons, of the type which are commonly utilized in emulsifier compositions. These include, among others, benzene, toluene, xylene, aromatic naphthas, methylated naphthalenes, tetrahydronaphthalene, cyclohexane, kerosene, dipropylene glycol methyl ethers, and n-propanol. These and various other organic solvents are frequently sold under trade names such as Cyclosol 53, which is a xylene type solvent; "Sovacide 544C," which is an aromatic petroleum oil containing methylated naphthalenes: Varsol, which is a straight petroleum solvent; Certrex 47 (which is a highly aromatic oil); and Solvesso 150, which is derived from petroleum and has a high content of aromatic hydrocarbons. Still other organic solvents which can be used in the emulsifier compositions of the present invention are disclosed in various of the patents referred to below. The acetonitrile is generally utilized in proportions of the order of 1 to 20%, by weight, and particularly desirable from 2 to 8%, of the emulsifier composition as a whole. When the content of normally solid nonionic emulsifier is at least 50%, by weight, of the emulsifier content of the emulsifier composition, it is particularly desirable that the acetonitrile be present in proportions of at least and, better still, from 5 to 10%, by weight, of the emulsifier composition as a whole. In terms of proportions based on the total organic solvent content used in the emulsifier compositions, the acetronitrile may comprise at least 10% and, better still, of the order of to 50%, by weight, of: the organic solvent content and, indeed, as stated above, even all of the organic solvent content. In toxicant concentrate made by utilization of the emulsifier compositions of the present invention, the acetonitrile will be present in proportions in the range of 0.04 to 2% and, better still, in the range of 0.1 to 0.8%, by weight, of the toxicant concentrate composition as a Whole.

Nonionic emulsifiers useful in emulsifier compositions, and toxicant concentrates containing the same, to which my present invention relates are disclosed. by way of example, in US, Patents Nos. 2,447,475; 2,509,233; 2,552,187; 2,588,318; 2,731,338; 2,872,368; 2,875,128; 2,993,830; 3,046,153; 3,071,550; 3,074,791; 3,095,353; 3,097,173; 3,098,789; and Resissue No. 24,184.

While in the nonionic emulsifiers which are utilized in the emulsifier compositions of my present invention, the hydrophobic portion of the molecule is generally an alkyl or monocarboxylic, particularly fatty, acid acyl radical, this need not be the case. The hydrophobic portion of the molecule may be imparted by recurring oxypropylene, oxybutylene and higher oxyalkylene groups. Thus, for instance, the hydrophobic function may be achieved by six or more recurring oxypropylene groups -CH2CIIO (911: n

where n is at least 6 so that the polyoxypropylene radical will contain at least 18 carbon atoms. Where the polyoxyalkylene radical is oxyhexylene, the number of such recurring groups may be as low as 3 and, again, therefore, the oxyalkylene radical will contain at least 18 carbon atoms. Typical nonionic emulsifiers of this latter type are those disclosed, by way of illustration, in Patents Nos. 2,674,619 and 2,875,128, the nonionic emulsifiers of said last-mentioned patent being in the form of oxyethylated-oxypropylated glycerine wherein polyoxypropylene chains are attached to the glycerine nucleus and polyoxyethylene chains are in turn attached to said polyoxypropylene chains, the terminal groups being hydroxyl groups of the polyoxyethylene chains, the oxypropylene groups forming 48% to 66% of the total oxyalkylene groups, the oxyalkylated glycerine containing about 83- 126 mols of propylene oxide per mol of glycerine and further containing about 48-135 mols of ethylene oxide per mol of glycerine. In place of glycerine, other aliphatic polyhydric alcohols can be used for the polyoxypropylation-polyoxyethylation reaction to produce the nonionic emulsifiers of this particular type, among such polyhydric aicohols being ethylene glycol, diethylene glycol, polyglycerols such as diglycerol, triglycerol, tetragycerols and mixtures thereof, sorbitol, mannitol, arabitol, sorbitan, mannitan, pentaerythritol, dipentaerythritol, and the like.

While polyoxypropylene, polyoxybutylene and higher polyoxyalkylene groups can be present in the molecule of the nonionic emulsifier, there must be in all cases sufiicient polyoxyethylene groups in the molecule of the nonionic emulsifier to render the same either water-soluble or readily water-dispersible irrespective of whether the hydrophobic portion of the molecule is represented by alkyl radicals or monocarboxylic acid acyl radicals containing from 8 to 26 carbon atoms, or alkylated aryl radicals containing from 12 to 26 carbon atoms, or polyoxyalkylene radicals in which the recurring oxyalkylene groups thereof contain from 3 to 6 carbon atoms and in which any said polyoxyalkylene radicals contain at least 3 of such recurring oxyalkylene groups, generally derived from 1,2-propylene oxide or higher alkylene oxides or a-epoxides such as butylene oxide, pentylene oxide and hexylene oxides, or combination of such radicals,

The nonionic emulsifiers whose use is contemplated by my present invention are those which are water-soluble to readily waterdispersible and which are soluble in acetonitrile, or in the combination of organic solvents containing acetonitrile where the acetonitrile is used in admixture with other organic solvents, particularly hydrocarbon solvents, at the temperatures involved, namely, the temperatures at which the compositions are used or to which they are subjected in storage, transportation or shipping or the like.

Among such nonionic emulsifiers are alkyl phenoxy polyoxyethylene ethanols, ethylene oxide condensates, polyoxyethylated fatty alcohols, polyethylene glycol esters of fatty acids, alkyl aryl polyoxyethylene ethers, polyoxyethylene alkyl alcohols, polyoxyethylated vegetable oils, polyoxyethylene sorbitan esters of fatty acids, alkyl ethers and thioethers of polyoxyethylene glycols monocarboxylic and particularly fatty acid esters of polyoxyethylene gylcols, where the alkyl, fatty alcohol, fatty acid radicals contain from 8 to 26 carbon atoms, and there are present in the molecule of the nonionic emulsifier sufficient oxyethylene groups, at least 8 in number, to render said nonionic emulsifier water-soluble to readily water-dispersible.

While the emulsifier compositions contemplated by the present invention in its broadest aspect may comprise one or more nonionic emulsifiers of the type described above dissolved in acetonitrile, its major advantages reside in emulsifier compositions containing, in addition to one or more of the aforesaid types of nonionic emulsifiers, one or more anionic emulsifiers, preferably one or more watersoluble or somewhat water-dispersible anionic emulsifiers and one or more organic solvents in addition to the acetonitrile. The anionic emulsifier selected should be soluble in the mixture of ingredients making up the emulsifier composition as a whole, as well as in the toxicant concentrate compositions in which said emulsifier compositions are incorporated.

Anionic emulsifiers of the type which are utilized in the emulsifier compositions of my present invention are well known in the art and illustrative examples thereof have been referred to above. They are disclosed in large numbers of patents and other publications. Various of the patents mentioned above in connection with disclosures of known nonionic emulsifiers also disclose typical anionic emulsifiers which can be used in the emulsifier compositions, and toxicant concentrates containing the same, with which my present invention is concerned, and additional anionic emulsifiers are disclosed in numerous other patents of which the following may be mentioned: 2,976,209; 2,976,211 and 3,080,280.

Where anionic emulsifiers are used together with the aforesaid types of nonionic emulsifiers, generally speaking, in most cases the nonionic emulsifier or emulsifiers will be used in amounts in excess of the amounts of the anionic emulsifier or emulsifiers. However, this may vary, and the amount of the anionic emulsifier or emulsifiers may be greater than the amount of the nonionic emulsifier or emulsifiers in certain systems for optimum results. In general. the ratio by weight, of the nonionic emulsifier or emulsifiers to the anionic emulsifier or emulsifiers may range from 95:5 to 5:95 with a particularly useful range of ratios, in most cases, from 75:25 to 25:75.

Numerous toxicants which can be utilized to produce toxicant concentrates containing the emulsifier compositions of my invention are well known in the art. They include, among others, chlordane, aldrin, dieldrin, lindane, heptachlor, nemagon, DDT, toxaphene, methoxychlor, alkyl aryl sulfite (Aramite), organic thiocyanates such as B-butoxy, B-thiocyanodiethyl ether, lower alkyl ethers of pentachlorophenol, parathion, malathion, p-nitrophenylthiophosphoric acid diethyl ester, DDVP (dimethyldichloro-vinyl phosphate), pbosdrin (dimethylcarbomethoxy methylvinyl phosphate) and bidrin (dimethyl phosphate of 3-hydroxy-N,N-dimethyl-cis-crotonamide). Generally speaking, the toxicants with which the emulsifier compositions of my invention are utilized are of the type which are organic solvent-soluble and substantially insoluble or difiicultly dispersihle in water. However. toxicants such as DDVP, phosdrin and bidrin are soluble in water but they must be formulated as solutions in organic solvents, generally water-insoluble organic solvents, since, in aqueous solutions, they readily hydrolyze. For convenience of expression, therefore, where reference is made herein and in the claims to toxicants which are organic water-insoluble toxicants, it will be understood that such terminology is intended to encompass toxicants which are organic solvent-soluble and substantially insoluble or difficultly dispersible in water, as well as toxicants. exemplified by DDVP, phosdrin and bidrin, which, although technically soluble in water, require formulation in the form of organic solvent solutions to avoid hydrolysis or other breakdown of the toxicant. The foregoing, and others, are disclosed in the various patents referred to above.

The following examples are illustrative of emulsifier compositions falling within the scope of my invention. Other specific embodiments will readily occur to those skilled in the art in the light of the guiding principles and teachings disclosed herein. All parts listed are by weight:

EXAMPLE 1 Parts Aminoethylethanolamine salt of monododecyl benzene monosulfonic acid (76% solution in n-propanol) 12.4 -mol ethylene oxide adduct of nonyl phenol 38.8 -mol ethylene oxide adduct of nonyl phenol 2.58 Xylene 12.5 N-propanol 5 Acetonitrile 5.5

EXAMPLE 2 Parts Aminoethylethanolamine salt of monododecyl benzene monosulfonic acid (76% solution in n-pro- 6 EXAMPLE 3 Parts lsopropylamine salt of monododecyl benzene monosulfonic acid 30 Triton X455 (al kyl phenoxy polyethoxyethanol;

US. Re. 24,184 of July 24, 1956) 50 Xylene 10 Acetonitrile l0 EXAMPLE 4 Parts Half ammonium half isopropylamine salt of the sulfosuccinic acid ester of the oleic acid amide of monoisopropanolamine 28 Antarox A400 (alkyl phenoxy polyethoxyethanol;

U.S. Re. 24,184 of July 24, 1956) 45 Cyclosol 53 15 Xylene 7 Acetonitrile 5 EXAMPLE 5 Parts Sodium salt of polyoxyethylene ether monosulfonate of tertiary octyl phenol (about 17 mols of ethylene Calcium salt of monododecyl benzene monosulfonic acid 37.5 15-mol ethylene oxide adduct of nonyl phenol 32 20-mol ethylene oxide adduct of nonyl phenol l6 Aromatic solvent ("Cyclosol 53) 11.5 Acetonitrile 3 EXAMPLE 8 Parts Aminoethylethanolamine salt of monododecyl benzene monosulfonic acid 39.4 l5-mol ethylene oxide adduct of nonyl phenol 11.3 20-mol ethylene oxide adduct of nonyl phenol 29.1 Aromatic solvent (Cyclosol 53") 15.2 Acetonitrile 5 EXAMPLE 9 Parts Aminoethylethanolamine salt of monododecyl benzene monosulfonic acid 46.5 Butoxy ethoxy polypropoxypolyethoxy ethanol l4 12-mol ethylene oxide adduct of nonyl phenol 5 l5-mol ethylene oxide adduct of nonyl phenol 11.5 Aromatic solvent (Cyclosol 53) 20 Acetonitrile 3 EXAMPLE 10 Parts l5-mol ethylene oxide adduct of nonyl phenol 50 20-mol ethylene oxide adduct of nonyl phenol 35 Acetonitrile l5 EXAMPLE 11 Parts 50-mol ethylene oxide adduct of castor oil Acetonitrile 20 7 EXAMPLE 12 Parts Toxaphene 60 Calcium salt of monododecyl benzene sulfonic acid 2.5

Refined tall oil fatty acid-18-mol ethylene oxide adduct 2.5 Kerosene 39 Acetonitrile 1 EXAMPLE 13 Parts DDT 25 Aminoethylethanolamine salt of monodecyl ben- Nonionic emulsifier prepared by reacting 1 mol of glycerine with 60 mols of 1,2-propylene oxide followed by reacting with 60 mols of ethylene oxide- 3 Xylene 75 Acetonitrile 2 What is claimed as new and desired to be protected by Letters Patent of the United States is:

1. A toxicant concentrate comprising an organic waterinsoluble toxicant dissolved in an organic solvent and containing (a) an acetonitrile-soluble and water-soluble to readily water-dispersible nonionic emulsifier containing in the molecule thereof (1) a hydrophobic group selected from the group consisting of alkyl and monocarboxylic acid acyl containing from 8 to 26 carbon atoms, alkylated aryl containing from 12 to 26 carbon atoms, and polyoxyalkylene in which the recurring oxyalkylene groups thereof contain from 3 to 6 carbon atoms and in which said polyoxyalkylene contains at least 18 carbon atoms, and (ii) sufficient oxyethylene groups, at least 8 in number, to render said nonionic emulsifier water-soluble to readily water-dispersible, said organic solvent being acetonitrile, said acetonitrile constituting from 0.04 to 2%, by weight, of said toxicant concentrate.

2. A toxicant concentrate in accordance with claim 1, said composition also containing an anionic emulsifier and a hydrocarbon solvent.

3. A composition according to claim 2 wherein the ratio of the nonionic emulsifier to anionic emulsifier is :5 to 5295.

4. A composition according to claim 3 wherein the acetonitrile is from 15-50% of the total solvent.

5. A composition according to claim 2 wherein the acetonitrile constitutes 0.1 to 0.8%, by weight, of said toxicant concentrate.

6. A toxicant concentrate comprising a solution of an organic water-insoluble toxicant, (a) a 15 to 20 mole ethylene oxide adduct of nonyl phenol, and (b) a watersoluble to readily water-dispersible C to C alkyl benzene sulfonate, dissolved in (c) acetonitrile and (d) a hydrocarbon solvent, said acetonitrile constituting from 0.1 to 0.8%, by Weight, of said toxicant concentrate.

7. A toxicant concentrate comprising a solution of an organic water-insoluble toxicant and (a) an acetonitrilesoluble and water-soluble to readily water-dispersible nonionic emulsifier which is an oxyethylated-oxypropylated glycerine wherein poly oxypropylene chains are attached to the glycerine nucleus and polyoxyethylene chains are in turn attached to said polyoxypropylene chains, the oxypropylene groups forming 48% to 66% of the total oxyalkylene groups, the oxyalkylated glycerine containing about 83-126 moles of propylene oxide per mole of glycerine and further containing about 48- moles of ethylene oxide per mole of glycerine, in (b) acetonitrile, said acetonitrile constituting from 0.04 to 2%, by weight, of said toxicant concentrate.

References Cited UNITED STATES PATENTS Re. 24,184 7/1956 Sanders et al l6742 2,319,996 l/l958 Riley l6742 2,872,368 2/1959 Sanders et a1. l6742 2,946,721 7/1960 Hyatt et al. l6742 3,036,130 5/1962 Jackson et a1 252351 X 3,098,789 7/1963 Littler. 3,108,038 10/1963 Fielding et al. 3,145,139 8/1964 Fearing.

ALBERT T. MEYERS, Primary Examiner.

V. C. CLARKE, Assistant Examiner.

US. Cl. X.R. 167-l70; 252351