US2161462A - Composition of matter - Google Patents

Description

. Patented June a, 1939 UNITED STATES PATENT OFFICE COMPOSITION OF MATTER Albert L. l 'lenner, Wilmington, DeL, assignor to E. I. du Pont de Nemom's & Company, Wilming'ton, Del, a corporation of Delaware No Drawing. Application July so, 1938,

- Serial No. 222,217

16 Claims. (01. 107-22) 7 This invention relates to compositions of matter for use in preparing horticultural sprays and more particularly to compositions containing a finely divided water-insoluble active solid in- 5 gredient intimately mixed with an aliphatic alcohol containing from eight to fourteen carbon atoms.

In most suspensions used as horticultural sprays the finely divided, water-insoluble solid ingredient is causedto' wet out by incorporating, either in the water or in the solid material, a substance which lowers the surface tension of the "dispersing medium. Usually such materials have .a highly detergent action which, coupled ,15 with the lowering of the surface tension, causes heavy run-oi! of the spray from the sprayed plant.

In view of the abnormal run-ofi caused by the use of such wetting agents, horticultural go sprays are frequently applied in the form of simple aqueous suspensions. The preparation and application of such suspensions, particularly from materials diflicultly wetted bywater, requires the use of special power sprays of a 25 capacity available to large producers only.

I have found that by intimately mixing a finely divided, water-insoluble active solid ingredient with a higher aliphatic alcohol containing at least eight carbon atoms a product is obtained which 40 uble active solid ingredient causes the majority of individual particles to be wetted, at least in part, with a film ofthe alcohol, which film due t'o the presence of hydroxyl groups imparts wetj ting out properties to the finely divided material. '45 Compositions according to this invention possees the further advantage that they may be easily prepared simply by thoroly mixing the finely divided, water-insoluble active solid with an aliphatic alcohol containing more than eight 50 carbon atoms by suitable mixing apparatus such alcohol to give the following composition: 45

as a ball mill. The product soprepared retains its 'dry and finely divided form so that it may be marketed and transported at a minimum of cost.

In order that my invention may be more fully understood reference may be had to the following specific examples:

Example I According to this example 99 parts of sulfur ground to 300 mesh was thoroly mixed with one part of decyl alcohol in a all mill to give the following composition:

I Percent Sulfur-ground to 300 mesh 99 Decyl alcohol 1 Example II In a like manner 99 parts of, thio-diphenylamine ground to 200 mesh was thoroly mixed with one part of decyl alcohol to give the following composition:

. Per cent Tlfio-diphenylamine-ground to 200 mes 99 Decyl alcohol 1 The compositions of Examples I and II were easily dispersible in water and formed suspensions suitable by application to foliage by standard spray equipment. I

In some instances it is desirable to increase the stability and dispersibility of the suspension. For this purpose a small amount of a finely divided inert solid may be incorporated in the mixture. These inerts also act as conditioning agents to prevent caking or agglomerating during storage. The following examples are illustrative:

- Example III Using a ball mill as in Example I, finely ground sulfur mixed with celite was milled with decyl Per cent sulfur-ground to 300 mesh 95 celite v 4 Decyl alc h l I Example IV In a similar manner the following composition was prepared:

Per cent Tetra-methyl-thiuram-disulflde-ground to 300 mesh 80 Bancroft clay 19 Decyl alcohol 1 The compositions of Examples III and IV wetted out well in water and formed suspensions readily by stirring the mixture into a suitable quantity of water.

As some tendency toward flocculation was observed in sprays prepared from the composition of Example IV it was found desirable to include a small amount of a defiocculating agent. For this purpose a small amount of a sulfonate condensation product of naphthalene and formaldehyde was incorporated, as illustrated in the following example: I

Example V Per cent Tetra-methyl-thiuram-disulfide 80.0 Bancroft clay 18.8 Decyl alcohol 0.7

Sulfonated condensation product of naphthalene and formaldehyde 0.5

While I have specifically disclosed decyl alcohol in Examples I thru V, I prefer for economic reasons to employ technical dodecyl alcohol such as obtained by the hydrogenation of coconut oil acids. Such alcohol consists predominately of dodecyl alcohol but contains minor amounts of octyl, decyl, and tetradecyl alcohols.

In some cases it has been found desirable to include conditioning agents adapted to enhance the free flowing qualities of the composition. This is especially desirable with compositions containing thio-diphenylamine. While for the most part inerts such as celite and Bancroft clay satisfactorily perform this function, material improvement, especially in the case of thio-diphenylamine, is obtained by the inclusion of tricalcium phosphate as illustrated in the following example:

Example V-I Per cent Thio-diphenylamine 86.0-94.2 Technical dodecyl alcohol 0.4- 2.0 Tricalcium phosphate 5.0-10.0

Sulfonated condensation product of naphthalene and formaldehyde 0.4- 2.0

If desired the tricalcium phosphate may be replaced in part by other inerts such as celite. Preferably, however, the tricalcium phosphate should not be less than about 1.0 per cent. A suitable composition is illustrated in the following example:

This composition has been found especially well adapted for preparing sprays used in the control of the codling moth. It disperses readily in water, forms a suspension sufficiently stable for spray purposes, is a free flowing powder easily handled in the preparation of sprays, and retains these properties during storage.

.combinations of these effects.

In place of tricalcium phosphate I may use other water-insoluble phosphates such as dicalcium phosphate.

In using certain of these alcohols, notably tetradecyl alcohol, which are solid at room temperature, it is advisable to carry out the mixing at a temperature sufliicent to liquefy the alcohol. This procedure is illustrated by the following example:

Example VIII According to this example 99 parts of thiodiphenylamine were mixed with one part of tetradecyl alcohol and uniformly heated to a temperature of about 50 C. This mixture while still warm was introduced into a ball mill and thoroly mixed as in Example I without further heating. The product obtained was comparable in all respects to that of Example II, no difference in the wetting-out properties being discernible.

It is to be understood that the foregoing examples are given by way of illustration and variations may be made not only with respect to the nature and amounts of the essential ingredients as illustrated in Examples I, II and VIII, but also in respect to the nature and amounts of other ingredients which may be included to modify the properties of the mixture as illustrated in Examples III, IV, V, VI, and VII, so long as such variations do not depart from the spirit of this invention, wherein wetting-out properties are imparted to a finely-divided, water-insoluble active solid ingredient by intimately mixing therewith an aliphatic alcohol containing from eight to fourteen carbon atoms.

The alcohols useful for the purpose of this invention comprise the aliphatic alcohols containing from eight to fourteen carbon atoms, saturated or unsaturated, straight or branched chain, and acyclic or alicyclic. They may be used in any amount consistent with good wettingout properties and a dry marketable product. Too much will impart stickiness to the product and too little will give a product which is difficult to disperse, depending upon the nature of the finely divided, water-insoluble active material used and the nature of such inert material as may be used. I have found from about 0.4 to about 2.0 per cent to be practical operating limits, altho it is to be understood that wetting out properties may be imparted to finely divided inert active material by the use of more or less than that amount, as long as the majority of the particles of the active material are indi- .vldually wetted, at least in part, with a film of an aliphatic alcohol containing from eight to fourteen carbon atoms.

By a proper selection of inert conditioning agents, among which may be mentioned, in addition to those given by way of illustration, such inerts astripolite, kieselguhr, China clay, Bancroft clay, bentonite,kaolinite,talc,and tolonite, various effects may be obtained. Thus inerts may be employed to enhance the free-flowing properties of the composition and to prevent caking or agglomeration during storage, to improve the dispersing properties in water, to modify the character of the spray residue or to obtain various For example, a composition containing 50 per cent tetra-methylthiuram-disulflde, 25 per cent bentonite, 24 per cent Bancroft clay, and 1 per cent technical dodecyl alcohol illustrates a combination of these effects and is particularly desirable in that it provides amvy retentive spray residue on the sprayedi'oliage. The inert conditioning agents.

Examples V, VI, and VII. Similar .results may be.

obtained with other non-detergent dispersing agents such as goulac, glue, gelatin, and casein.

- Such materials as exercise appreciable detergent action or lowering of the surface tension are undesirable for this purpose.

According to this invention, aliphatic alcohols v are useful for imparting wetting-out properties to a largevariety of water-insoluble active solids and are particularly useful in this respect in admixture with active materials such as sulfur, thio-. diarylamines and thiuram sulfides, which not only are insoluble in water but also exhibit pronounced hydrophobic properties. Wetting-out and dispersing properties may be imparted to any waterinsoluble solid capable of being wetted by an allphatic alcohol containing from eight. to fourteen carbon atoms.

As previously indicated, the wetting-out property imparted to the finely divided, water-insoluble active solid by an aliphatic alcohol containing from eight to fourteen carbon atoms is probably due to the formation of a film of the alcohol on or about the individual particles and finely divided active solid. As the fine state of subdivision of the active material creates a surface which is inordinately large with respect to the mass of the active material such a film would necessarily be of the order of a mono molecular film. The presence of such a film, tho difilcult to establish as a fact, is consistent with generally acceptedviews with respect to analogous phenomena.

In view of the fact, however, that the presence of such a film can be proved only with difficulty, and in view of the fact that reputable authorities maydisagree as to the existence of such a film,-

I do not intend that my invention be limited by the particular theory which I have advanced or by any other particular theory. Consequently, reference to the presence of the aforementioned film on or about the individual particles of the finely divided active solid is intended only as a measure of the thoroughness with which the alcohol and thefinely divided active solid are in- July 3, 1937.

I claim:

1. A composition of matter in the form of a dispersible free-flowing powder for use in preparing horticultural sprays comprising a finely divided, water-insoluble active solid intimately mixed with an aliphatic alcohol containing from eight to fourteen carbon atoms.

2. A composition of matter in the form of a dispersible free-flowing powder for use in preparing horticultural sprays comprising a finely divided, water-insoluble active solid and a finely divided inert solid intimately mixed with an aliphatic alcohol containing from eight to fourteen carbon atoms.

3. A composition of matter in the form of a dispersible free-flowing powder for use in preparing horticultural sprays comprising finely dlvided sulfur intimately mixed with an aliphatic 8160:1180] containing from-eight to fourteen carbon ato 4. A composition of matter in the form of a, dispersible free-fiowing powder for use in preparing horticultural sprays comprising finely divided sulfur and a finely divided inert solid intimately mixed with an aliphatic alcohol containing from eight to fourteen carbon atoms.

51 A composition of matter in the form of a dispersible free-flowing powder for use in prepare ing horticultural sprays comprising finely divided thiodiphenylamine intimately mixed with an aliphatic alcohol containing from eight to fourteen carbon atoms.

6. A composition of matter in the form of a dispersible free-flowing powder for use in-preparing horticultural sprayscomprising finely divided thio'dlphenylamine and a finely divided inert mixed with an aliphatic alcohol containing from eight to fourteen carbon atoms.

8. A composition of matter in the form of a J dispersible free-flowing powder for use in preparing horticultural sprays comprising finely divided tetra-methyl-thiuram-disulfide and a finely divided inert solid intimately mixed with an allphatic alcohol containing from eight to fourteen carbon atoms.

9. A composition of matter in the form of a v dispersible free-flowing powder for use in pre paring horticultural sprays consisting essentially of finely divided sulfur and a minor amount of a finely divided inert solid intimately mixed with about 0.4 to about 2 per cent of technical dodecyl alcohol.

11. A composition of matter in the form of a dispersible free-flowing powder for use in preparing horticultural sprays consisting essentially of finely divided tetra-methyl-thiuram-disulfide intimately mixed with about 0.4 to about 2 per cent of technical dodecyl alcohol.

12. A composition of matter in the form of a dispersible free-flowing powder for use in preparing horticultural sprays consisting essentially of finely divided tetra-methyl-thiuram-disulfide and a minor amount of a finely divided inert solid intimately mixed with about 0.4 to about 2 per cent of technical dodecyl alcohol.

13. A composition of matter in the form of a dispersible free-flowing powder for use in preparing horticultural sprays consisting essentially of finely divided thio-diphenylamine and a minor amount of a finely divided inert water-insoluble solid intimately mixed with about 0.4 to about 2 per cent of technical dodecyl alcohol.

14. A composition of matter in the form of a dispersible free-flowing powder for use in preparing horticultural sprays consisting essentially 16. A composition of matter in the form of a dispersible free-flowing powder for use in preparing horticultural sprays having essentially the following composition: 1 Per cent Thio-diphenylamine 92 Technical dodecyl alcohol 1 Celite 5 Tricalcium phosphate 1 Sulfonated condensation product of naphthalene and formaldehyde ALBERT L.