AU594053B2 - Thermally stabilized bis alkylthio-alkylimino-n-alkyl carbamates - Google Patents

Description

4 llimlill\l tokkKKI1111, 4;1)HP11RAT1(1N AU-A 56 964 /86 PCT WORLD i '.LE L P Eur INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 86/ 05950 A01N 47/24, 25/22 Al (43) International Publication Date: 23 October 1986 (23.10.86) (21) International Application Number: PCT/USS6/00776 (81) Designated States: AT (European patent), AU, BE (European patent), BR, CH (European patent), DE (Eu- (22) International Filing Date: 17 April 1986 (17.04.86) ropean patent), FR (European patent), GB (European patent), IT (European patent), JP, KR, LU (European patent), NL (European patent), SE (European (31) Priority Application Number: 724,556 patent).

(32) Priority Date: 18 April 1985 (18.04.85) Published (33) Priority Country: US With international search report.

Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt (71) Applicant: UNION CARBIDE CORPORATION [US/ of amendments.

US]; 39 Old Ridgebury Road, Danbury, CT 06817

(US).

(72) Inventor: MILES, David, Lucas 112 Princeton Road, Chapel Hill, NC 27514 (US).

(74) Agent: COON, Gerald, Union Carbide Corpora- 4 DEC 1986 tion, Law Department E134, 39 Old Ridgebury Road, Danbury, CT 06817 AUSTRALIA

AUSTRAIAN

his documnt conl s te 5 NOV 1986 amendments made unu. r V98 SSection 49 and is correct for PATENT OFFICE (54) Title: THERMALLY STABILIZED BIS ALKYLTHIO-ALKYLIMINO-N-ALKYL CARBAMATES (54) Title': THERMALLY STABILIZED BIS ALKYLTHIO-ALKYLIMINO-N-ALKYL CARBAMATES

IV

(57) Abstract Sulfur-linked bis alkylthio alkylimino N-alkyl carbamate pesticides can be stabilized against thermal decomposition induced and accelerated by a variety of contaminants by incorporation of a substantially non-alkaline inorganic compound, containing at least two oxygen atoms bound to a multivalent cationic atom. Thermally stable wettable powder, dispersible granular and liquid formulations of these pesticides can be prepared.

This docuicmnt ct aini s the amendments imade under Section 49 and is correct for _1 -i WO 86/05950 PCT/US86/00776 1 THERMALLY STABILIZED BIS ALKYLTHTO-ALKYLAMINO-N-ALKYL

CARBAMATES

Field of the Invention This invention relates to thermal stabilization of alkylthio-alkylimino carbamate pesticides. More particularly, it relates to the retardation or prevention of thermal decomposition of sulfur-linked bis alkylthio-alkylimino carbamates by incorporation of multioxygen inorganic compounds into formulations containing these pesticides.

Background of the Invention Sulfur-linked bis alkylthio alkylimino-N-alkyl carbamate pesticides of the formula 0 C N 0 C N S S2

SR

3 R1 2 have a wide range of uses in controlling insects and other agronomic pests. Active compounds exhibit a very high level of pesticidal activity and substantially reduced mammalian toxicity and phytotoxicity when compared to other pesticidal compounds having a comparable spectrum of activity against the above mentioned pests.

These compounds are thermally unstable in the presence of a variety of contaminants. Heavy metals and their salts, particularly chloride salts, i are especially undesirable. Decomposition is extremely severe in the presence of copper metal, 1 Si 4

I

WO 86/05950 PCT/US86/00776 2 copper chlorides, ii:on metal, iron chlorides and iron oxide the form of rust. Other problematic metals include cobalt, nickel and aluminum.

Concentrations of as little as 10 ppm are effective if given enough time at temperatures of 60°C or higher. Sulfur and sulfide salts can also induce decomposition, although usually at rates slower than those of chloride-containing systems. Some organic decomposition initiators have also been identified, including pyridine, pyridine hydrochloride, di- and trisulfides, amines, peroxides and acids (e.g.

acetic and citric acids). Presence of 5% or more methomyl or its oxime can also induce decomposition.

The principal object of this invention to provide a method to inhibit or retard the thermal decomposition processes that may occur in bulk quantities of sulfur-linked bis alkylthioalkylamino-N-alkyl pesticides .when they are dried at elevated temperatures or stored for extended periods of time, especially in warmer climates. It is a further object to provide stable wettable powders and dispersible granular formulations of these ipesticides.

Detailed Description of the Invention This invention provides a method of retarding or inhibiting thermal decomposition of pesticides of the formula 0 If C C -N

S

SR

3

R

1 2 j

(I)

~I

~Pi

I

i j

I!

I 94 9 wherein R 1 is alkyl containing from one to five carbon atoms; R2 is alkyl, alkylthio, alkoxy, alkanoyl or alkoxycarbonyl, preferably all of which may contain from one to five carbon atoms and which may be unsubstituted or aliphatically substituted in any combination with one or more cyano, nitro, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxy or

R

4

R

5 -NCO- groups; or R 2 is phenyl, R 4

R

5 -NCO- or R 6

CON(R

4 wherein R and R 5 are individually hydrogen or alkyl, R 6 is hydrogen, alkyl or alkoxy; and R 3 is hydrogen, cyano, alkyl or alkylthio containing from one to five carbon atoms; provided that the total number of carbon atoms in R 2 and R 3 does not exceed eight and preferably further provided that when o R2 is alkyl substituted with alkylthio, R 3 is alkyl, the inhibition or retardation of thermal decomposition of this 75: compound being achieved by mixing the pesticide with 1- Jta 2% by weight of an inorganic phsophate type compound so as S to get a solid mixture.

Thsi invention also provides a solid or a substantially free of water pesticidal composition which compises: a pesticidally effective amount of a pesticide compound of the formula set forth above and an inorganic *prom o-o to phosphate type compound in an amount of -sJ 2% by weight to retard or inhibit thermal decomposition of said compound.

S

S

*S.S

S

9

S

54

K

3 111 r' i WO 86/05950 PCT/US86/00776 4 A. Definitions The term "powdered or granular composition" embraces all solid formulations which range in size from fine dusts those which pass through U.S.

Sieve screens No. 400 up to No. 100) to substantial particles as large as 5 mm in their largest dimension those which pass through a No. 4 U.S. Sieve screen).

Ar" tib ngfaiy nnna)lirio inorgni compound" is one which, when dissolved or dispersed in water in an amount useful to this invention, does not create a pH greater than 9 or which can be buffered to a pH less than 9.

"Thiodicarb" is the generic name of a pesticide having the formula set forth below: 1 I! CH C N 0 C N S -N C N C CH 3 I I 3

SCH

3

CH

3

CH

3

SCH

3 The term "compatability agent" encompasses additives that permit different pesticides to be combined in a single liquid formulation. Such agents may be incorporated into solid or liquid compositions containing one or all of the pesticides/ to be combined.

B. Pesticides The organic compounds of this invention are alkylthio-alkylimino-N-alkyl carbamates. They are widely used to control a variety of insect pests.

They may be prepared by well known methods, such as those set forth in U.S. Patents No. 4,004,031 and 4,382,957.

WO 86/05950 PCT/US86/00776 5 In the preferred compounds of this invention R 1 and R 3 or alkyl and R 2 is alkyl or alkylthio. The compound thiodicarb is especially preferred for the practice of this invention.

C. Thermodynamic Stability Typical decomposition times for thiocarb in the presence of a variety of contaminants are shown in Table 1. Thfse data were collected using the following procedure. A one-gram sample of thiodicarb was intimately mixed ,ith the indicated weight percent of contaminant. The solid was placed in a test tube that was then covered with a rubber septum cap and immersed in a constant temperature bath maintained at 100 0 C. An uncontaminated standard was run under similar conditions.

Decomposition was manifested in a variety of forms.

Some samples exhibited a rapid change from solid to dark liquid; dense yellow smoke was usually observed. Others underwent gradual discoloration and moistening. In these experiments the time of decomposition was the point when the sample was a dark-brown semi-solid. Reported values were averages of several repetitions for each sample.

The destabilizing effect of methomyl and other sulfur compounds is apparent from Section B *tI i' wo 86/05950 WO 8605950PCT/US86/00776 -6 TABLE I STABILITY OF CONJTAMINIATHD THIODICARB STORED-AT 100*C Identity Contaminant A. ntandard B. AUtocatalytic Products Methomyl Methomyl oxime Methyltrisulfide Dimethyl disulfide c. Miscellaneous Impurities CuC1 2 FeCd 3 Benzoyl peroxide citric acid Acetic acid 2-Ethyihexanoic acid Pyr idine kmount of Time to Thiodicarb :ontaminant Decomposition at 100*C 1% 3% 1-3% 12-13 days 13 days days 7 days 3 days 7 hours 8 days 6 days 10 days 8-9 days 8-9 days 10 mins.

45 sec.

5 days 3-5 days 2 days 4-6 days 2 days 6-10 days 1-3 days 2 ppm 2% 3-300 ppm 3% 1 0% 1% 3% 1-3% 1% 3' 1-3% 1-3% r, WO 86/05950 PCT/US86/00776 i 7 of Table I. Thiodicarb is stable at low concentrations by weight or less) of one of its principal decomposition products, methomyl.

However, as the concentration of methomyl is raised, the rate of decomposition increases significantly.

Likewise, the effect of methcmyl oxime is also substantial. As amounts of other decomposition products, such as dimethyltrisulfide and dimethyldisulfide increase, the rate of decomposition is substantially accelerated.

In Section C of Table I are included results of studies using contaminants that might be introduced during the preparation or storage of the pesticidal substance. As mentioned previously, heavy metal ions, particularly copper and iron, are especially deleterious. Use of manufacturing equipment or storage containers made of these metals in forms that can corrode to produce deleterious salts should be avoided if at all possible. The other organic materials are included to demonstrate the effects that such compounds might have on the product if they should be present, e.g. because they are found in the solvents that are used in the manufacturing process.

The ability of certain silicon-based carriers to reverse the decomposition of contaminated thiocarb is apparent from Table II. In these experiments one-gram samples of thiodicarb were first contaminated with the indicated weight percents of cupric and ferric chloride and then intimately mixed with a variety of silicas and silicates. The samples were then placed'in test i 1 r 7 1 1 1 i J ~~'O86O59sOPC/US86/00776 tubes and immersed In water baths at 50*Co 70 0 C and 4 100 0 C until decomposition was observed; decomposition time was measured when the solid had turned into a dark brown liquid. All values represented averages of several repetitions. In some instances stabilization of several orders of magnitude was observed relative to standards containing no silica.

I

I

WO 86105950 PUS86/00776 9- Contaminan 1% CuC1 2 1% CuC1 2 1% CUC1 2 1% anti. Fe 1% anh. Fe 1% anh. Fe TABLz rI THXODXCARB STABILIZATION4 BY SXLICA-BASED CARRERS Time to Deomiposition at t stabilizer S50C 70*C >20 days 12 days 1 4 miiis.

10% Barden clay >19 hrs.

10% Celite >22 hrs.

C1 3 13-52 mins. C1 3 5% Hi-Sil 16-19 days 7-21 hrs.

C1.2 10% Hi-Sil >30 days 30-45 hrs. I 004 C 1-27 hrs.

mins.

miris.

mins.

rl WO086/05950 PCT/IUS86/00776 11 Thermodynamic instability wag more a accurately and reproducibly evaluated by detectionl of an exotherm in a dual thermocouple test conducted as follows. A test mixture was prepared by intimately mixing the pesticide standard and the desired quantity of stabilizer. (The pesticide standard was thiodicarb containing sulfur as a synthesis impurity; ii no additional contaminants were added.) A jf thermocouple was placed into two grams of dried sample in a measuring vial. A second thermocouple was placed in the vial one inch above the surface of the mixture. The vial was then placed in a heating block and heated as quickly as possible to 160 0 C; the rate of heating was not important as long as it was reproducible and the mixture reached 160 0 C before the exotherm occurred for untreated pesticide. The time to exotherm for the mixture was compared to that for an untreated standard, i.e. one containing pesticide alone. Measurements for a single mixture of additive and pesticide were usually taken five to ten times to assure reproducibility. In all cases the pesticide was taken from the same batch to avoid differences in contamination levels that are often observed from one batch to the next. The time to exotherm was directly proportional to the Ohrma tab~)ity the mixture* iv' inorganic compounds containing at least two oxygen atoms bound tc a multivalent cationic atom are surprisingly effective at retarding or inhibiting the occurrence of the exotherm in sulfur-linked carbamate pesticides such as thiodicarb. Included in this group are alkali metal WVO 8 6/059SOPT/06/07 404 monobasic phosphate# A motaphosphates, ZU WtJaf 0r ttsufU akal oalax:-AtJWneeat d ~taxid -ha.

fm 4 a r sicat.. The compounds chat are esrecially effective at retarding the exotherm are sodiumo~ potassium monobaoic phosphate# iiulnUt heax am at a ph o sp ha tea ,Mndzliphoriz ilUt-. Mixtures of those compounds are also effective. The abilities of 4nvunaL~of the preferred stabilizers to retard the exotherm In thiodicarb as measured in the dual thermcouple test described above are apparent from the results shown in Table XII.

These results indicate that -potassium monobasic phosphate is an especially preferred stabilizer for thiodicarb.

TIME TO EXOTHERM FOR STABILIZED T1410DUARB Tim~e to 9xo therm Additive (minutes2) 54 (standard) Na2S3~ 57. Na 2

SO

3 111 KHIP0 4 >300 3% NajHPO4 58 The decomposition of thiodicarb and the increasing concentration of methomyl have been monitored at 100 0 0 in the presence of sodium monobasic phosphate (Table IV). Samples of .M 1.J.w 9..

9

S

a 9.

.9 .9.

thiodicarb untreated and treated with varying amounts of sodium monobasic phosphate were maintained at 100°0 for several days. They were periodically analyzed by standard HPLC methods for thiodicarb and methomyl. As thiodicarb concentration decreased, methomyl concentration increased.

However, the results indicated that as the decomposition process continued, other products formed as well; the sum of the weight percentages of methomyl and thiodicarb became progressively smaller as decomposition proceeded. Increasing amounts of the monobasic phosphate appear to stabilize the thiodicarb as the decomposition reaction proceeds over several days; decomposition products, especially methomyl, accelerate the process. These results also support the hypothesis that bis alkylthio-alkylamino-N-alkyl carbamates 15 undergo an autocatalytic decomposition process involving a S number of sulfide species, also catalyze the process.

Stabilization of sulfur-linked bis alkylthio-alkylamino- N-alkyl carbamates is achieved by incorporating the stabilizers of this invention in amounts ranging from ljps La 2 percent by weight of total mixture. Although the concentration of a particular inorganic stabilizer must be evaluatedempirically.

S When the stabilizer is one of the above mentioned phosphate compounds, stabilization will be observed with as little as S 0.5 to l5% by weight.

9..

9 7 9

S

*b9

S

.9 9

S

9* 9 n 12 i 1~ i i i 7127 WO 86/05950 PCT/US86/00776 13 TABLE IV THIODICARB DECOMPOSITION AND METOMYL FORMATION IN THE PRESENCE OF NaH 2

PO

4 at 1000C Stabilizer 0.25%, NaH 2

PO

4 NaH 2

PO

4 1% NaH 2

PO

4 Thiodicarb Hethoinyl Thiodicarb Methornyl Thiodicarb Methoiuyl Thiodicarb I Me thony 1 -0 1 2 3 4 93.A 44.1 2B 0.3 12.3 12.1 93.1 82.0 78.8 54.5 0.3 2.5 5.7 12.2 93.1 81.7 77.6 55.7 56.0 0.3 3.6 8.3 8.2 12.9 93.1 81.6 85.9 84.8 63.9 0.3 2.2 3.9 4.3 ft WO 86/05950 PCT/US86/00776 14 D. Formulations The compositions of this invention may be applied as solids or as liquid dispersions or solutions to both field and turf to control pests.

Application is by methods readily known to those skilled in the art. Effective amounts range from about 0.05 to about 20 Ibs. per acre of active pesticide.

Formulations useful in the practice of this invention are solids, as wettable powders or dispersible granulars, and liquids, as solutions or dispersions. The preferred wettable powders and dispersible granular formulations comprise: (a) from about 1. to about 981 by weight of a bis alkylthio-alkylamino-N-alkyl carbamate. pesticide; inorqanic F__ from about 0.01% to about P& by weight of anr phospta0e. to uiL ll- ti l r ri. compound; mat -van from about 0.01% to about 20% by weight of wetting agent; and from about 1i to about 12% by weight dispersant.

Preferred liquid formulations comprise: from about 0.01% to about 751 by weight of a bis alkylthio-alkylamino-N-alkyl carbamate pesticide; norgani c_ from about 0 .Q0 01 1 to about Q% by weight of an"> pho'ihle ype set la. l nuna compound; Pcat from about 0.01% to Sabout 201 by weight wetting agent; from 0% to about 101 by weight dispersant; and from about 51 to about 801 by weight inert liquid carrier.

Suitable carriers include water, unsubstituted

I

ii. -i WO86/05950 PCT/US86/00776 15 aliphatic and aromatic hydrocarbons or analogues containing, for example, alkyl, halo or hydroxy substituents, fatty acids, and oils, such as linseed and cottonseed oil, derived from natural extracts.

Of the pesticides useful in this invention, the preferred compound is thiodicarb. The preferred phoOqhaLe PIpe.

xyg .e...ai.nm inorganic compounds are phpt aid_.and sodium or potassium monobasic phosphate,andc metaphosphate, phV'e. -lMjtsul a Many wetting agents, anionic, cationic or nonionic, are available for these formulations.

Illustrative wetting agents are alkali metal salts of fatty alkyl or alkenyl sulfates or sulfonates containing eight to twenty carbon atoms; alkali metal salts of alkylbenzyl or alkylnaphthyl sulfonates wherein the alkyl chain contains eight to twelve carbon atoms; ethoxylated alkylphenols wherein the alkyl groups contain eight to twelve carbon atoms; dialkylesters of sodium sulfonsuccinic acids wherein the dialkyl groups contain five to ten carbon atoms; or polyalkylene oxide modified dimethypolysiloxane in which the alkylene groups are ethylene or propylene or a mixture of both. Other suitable wetting agents may also be used.

Dispersants are materials which interact with solid ingredients in the formulations and the liquid medium that is used to suspend those solids for purposes of application. They must be soluble in that liquid phase and they usually behave as a binder for the solid powder or granular.

Representative dispersants useful in the practice of rf- 1 F_ I

I-U"~

0 000 0 1 0B 0O 0'

S.

this invention include starches, alkali metal or alkaline earth salts of lignin sulfonates; and condensates of alkali metal alkylnaphthalene sulfonates and organic compounds containing one to three carbon atoms and at least one oxygen atom, such as the condensate of formaldehyde and sodium naphthalene sulfonic acid.

An additional component particularly useful in the formulations of this invention is an antifoaming agent. It prevents or reduces foam during the preparation of the powder or granulars and during dispersion and application of the composition. It also stabilizes the resulting dispersion and permits more rapid redispersion if coagulation of solids occurs in a dispersion. An especially useful antifoamer is a S dialkylpolysiloxane. Particularly effective are 04 dimethylpolysiloxanes formulated as emulsions or pastes. Such additives donot act as stabilizers for the pesticides.

oa, A particularly preferred composition of the invention comprises 70% to 95% by weight thiodicarb, from 2% to 3% by weight of sodium salt of sulfonated lauryl acid, from 8% to by weight of a sulfonated naphthalene formaldehyde condensate, from 1% to 3% by weight of a dimethylpolysiloxane, and from 0.5% to 1.5% by weight sodium or potassium monobasic phosphate. The composition may also include a nonionic condensate of ethylene oxide and hydrophobic bases made by 02f condensing propylene oxide with propylene glycol.

Pesticidal formulations containing multiple pesticides are popular for the obvious reason of convenience--only one S application is necessary to deposit all of the actives. While many multiple formulations are easily prepared simply by mixing all of the active ingredients, the formulations of this invention may require the presence of a compatability agent that prevents flocculation in the final solution or dispersion that is applied to the target plants. The presence of an additional, chemically unrelated pesticide such as parathion may destabilize a dispersion prepared for spray 'C c 16- 1

I

0 0c 1 WO 86/05950 PCT/US86/00776 17 application. The preferred compatability agents for these compositions are condensates of alkylene oxide and hydrophobic bases made by condensing an alkylene oxide with an alkylene glycol wherein all aklyl substituents contain from two to four carbon atoms.

A particularly effective agent is a paste condensate of ethylene oxide with hydrophobic bases formed by condensing propylene oxide with propylene glycol.

A number of other well known ingredients can be incorporated into the wettable powders and dispersible granulars of this invention as the need arises, provided, of course, that they do not affect the ability of the inorganic compound to stabilize the pesticide or the stability and dispersibility or wettability of the powder or granular. These additives might include buffers, carriers or diluents, dyes, fragrances, humectants, thickeners, biocides and anti-evaporative agents.

The solid compositions of this invention can be prepared by various methods well known in the art, such as pan granulation, fluidized bed mixing 4nd drying, spray drying, intensive mixing agglomeration, extrusion, compaction or pelletizing. For pan granulation and fluidized bed processes, a mixture of dry ingredients :3 prepared and transferred into the mixing/drying chamber that contains water and any liquid ingredients; the slurry is thoroughly mixed and then dried.

Particles are then ground to a desired size. If a.spray drying process is used, grinding of the mixture of dry ingredients or of the slurry is preferred.

t r A7,. 1 ~D IP~)LYU XII I II~

I

WO 86/05950 PCT/US86/00776 18 The various processes yield solids containing a spectrum of particle sizes and moisture contents. A useful product is one which meets the particle size requirements for a particular application', which contains less than 5% by weight water, and preferably less than and which disperses well in water or oil. For granular compositions good dispersibility is obtained with particles retained on a U.S. Screen No. 100 (149 microns), and optimum particle stability is obtained with less than 2% moisture. Any particles that are too small, too large or too wet can be returned to the manufacturing or drying apparatus and recyled.

Preparation of the liquid compositions of this invention may be accomplished by methods known in the art. Useful dispersion formulations will not separate into liquid and solid phases during extended storage at ambient temperatures. To enhance stability the size of dispersed particles may be reduced by techniques, such as air and wet milling, known in the art.

The following examples are offered to illustrate useful formulations of this invention and to demonstrate the effects of various stabilizers.

EXAMPLE 1 To demonstrate the effect of a phosphate stabilizer in a dispersible granular, the following two formulations were prepared (by mixing ingredients in an aqueous slurry and spray drying to less than 21 water) and their thermal stability compared; (all values are percent by weight of the dry ingredients.

4 <1-

A

WO 86/05950 PCT/US86/00776 19 Formulation Formulation A B (no thermal) (thermal stabilizer) stabilizer) Ingredient 87.4% 86.8% thiodicarb 8.6 8.6 dispersant (sodium salt of sulfonated naphthylene formaldehyde condensate) 1.3 1.3 dispersant (starch) 2.5 wetting agent (sodium salt of sulfonated lauryl acid) 0.2 0.2 buffer (citric acid) 0.5 thermal stabilizer (NaH 2

PO

4 0.2 antifoamer (dimethylpolysiloxane emulsion) Time to Exotherm 46 mins. >120 mins.

It is clear that as little as 0.5% NaH2PO greatly enhances the thermal stability of this formulation. Formulation B can be stored for much longer times at elevated temperatures (approximately 45-55 0 C) than Formulation A, and Formulation B is much less likely to decompose during drying than is Formulation A.

EXAMPLE 2 ispersible granular stabilized with silica was prepare mixing 86.5% by weight thiodicarb containing approx e 3% silica and 3% sulfur; dispersants by weight h, 6.8 by weight sodium salt of sulfonatd naththalen i1 7 i Im.

WO 86/05950 PCT/US86/00776 20 C1YIlI 4~ -~ul~nrA l--k-rr -Jr pol alkylene glycol ether); wetting agent by weight ioctyl ester of sodium sulfosuccinic acid); antifoamer 1.0% by weight magnesium stearate); and buffer b weight citric acid). In this formulation stab zer silica) content was approximately 2.6% bysweight. The mixture was ground to a powder of aerage particle size less than 10 microns and then transferred to a fluidized bed chamber for mixing with wa r and subsequent drying.

After screening the product a range of -12 to +40 mesh Sieve size), it ha the following characteristics: CIPAC suspendibility 76%

I

-ftuti. -irfc-eY T--b .inu-ua EXAMPLE D A very stable sample containing two stabilizers jas prepared by slurrying, in water, the following ingredients (all weight percents are based on added weights of the ingredients except water): 86.1% thiodicarb containing 5% sulfur and silica; 10.1% dispersant (sodium salt of sulfonated naphthalene formaldehyde condensate); 2.5% wetting agent (sodium salt of a sulfonated lauryl acid); 0.6% antifoaming emulsifier (dimethylpolysiloxane emulsion); and 0.7% thermal stabilizer

(KH

2

PO

4 The slurry is wet ground to pass through a No. 325 screen Sieve size) and spray dried to a moisture content of less than 2%.

Approximately 95% of the resulting granular has a .4 WO 8605950PCr/U586/00776 -21 particle size distribution spanning the narrow range of -14 to +100 mesh Sieve size).

The gran~slar within this particle size range exhibits the following characteristics: CIPAC suspendibility 907.

Time to exotherm >120 minutes

Claims (15)

1. A method of retarding or inhibiting thermal decomposition of pesticides of the formula: 0 R 2 =N 0- 0 -N SR 3 R 1 2 wherein R 1 is alkyl containing from one to five carbon atoms; Rg is alky alkylthio, alkoxy, alkanoyl or alkoxycarbonyl, or R 2 is phonyl, R R -NCO- or R 6 CON(R 4 wherein R 4 and R S 10 are individually hydrogen or alkyl, R6 is hydrogen, alkyl or i alkoxy; and R, is hydrogen, cyano, alkyl or alkylthio S containing from one to five carbon atoms; provided that the i total number of carbon atoms in R and R does not exceed 2 3 eight, which comprises intimately mixing said pesticide with 2% by weight of an inorganic phosphate type compound so as to get a solid mixture.

2. A method according to claim 1, wherein each of alkyl, alkylthio, alkoxy, alkanoyl or alkoxycarbonyl of R 2 contains from one to five carbon atoms and is unsubstituted or 020 aliphatically substituted in any combination with one or more cyano, nitro, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxy S or R R 5 -NCO- groups; provided that when R 2 is alkyl substituted with alkylthio, R 3 is alkyl. S• 3. A method according to claim 1 or 2 wherein the mixing i is made in such a way so that the solid mixture is I substantially free of water. A method according to any one of claims 1 to 3 which comprises mixing said pesticide with from 0.5 toI-5% of the phosphate compound.

5. A solid pesticidal comprisiong which comprises: a. a pesticidally effective amount of an organic compound of the formula 0 S11 S22 4 R N 0 0 N- SR 3 R 1 2 wherein: R io alky containing from one to five carbon tomur; R to alkyl, alkylthio, alkoxy, alkanoyl or alkoxy earbonyl, ir A io phenyl, R 0100 4 or R 6 00(R 1 wherein: R and R are individually hydrogen or alkyl; R6 in hydrogen, alkyl or alkoxy; and R io hydrogen, cyano, or alkyl or alkylthio containing from one to five earbon atomo; provided that the total number of carbon atomo in and R dooe not exceed eight; and A 3 Sb. an inorganic phosphate type compound in an amount of 2% by weight to retard or inhibit thormal decomposition of oaid compound. A 0si 6. A oubatantially froee of water postlidal compoition which comprieo: a. a pesticidally effective amount of an organic compound of the formula 0 -R 0= N 0 C- I 2 wherein: R is alkyl containing from one to five carbon atoms; R is alkyl, alkylthio, alkoxy, alkanoyl or alkoxy- 02 carbonyl, or R 2 is phenyl, RR 5NCO- or R6GON(R :s owherein: R and R are individually hydrogen or alkyl; 4 5 R 6 is hydrogen, alkyl or alkoxy; and R3 is hydrogen, cyano, or alkyl or alkylthio containing from one to five carbon atoms; provided that the total number of carbon atoms in R2 and R does not exceed eight; and 3 b. an inorganic phosphate type compound, in an amount ,Rrom 0.,01 G- of Ji 4o 2% by weight to retard or inhibit thermal decomposition of said compound, A -23- t r 16 i 4 4.. 4 44l a .4 .4 4& *r 94 A Pootleidal POUnOOtion awwn to sn1~ whoroin Code of a114y, aehy tV.alo, thiao/ xywarbLonyl, g i kntii roi on. ton flVt oawnxIn &biin and io Unouottauvttd or alphatpIally !,o1 in ayv eo@Obinationi with Lino or noN. eyanic, 0l ro, aiV fythlc, a hyloufaguy1, alkyilo iYfony, 4U hofy o)r h I I groujMO; providoi that when i a n uloa Vtrtd wRt Ia rI 14if, R 3 Lolrt~

8. A ecot ielda1 eg tplofi e p fer"ng to any ncjl of claino to 7 who r(An the d61Vooff iinetRunt i0 fron 0.012 to 21' by weight.

9. Apoo eld l en ip itiul 'r Aeeoudgl to any one oif alaintS to 8 whoi'ein, in nad oreganic. O'binpun, ht I and R 3 are alkyl and hq io uly l rlkyilitio. VS 10. A peotioldal a-t Hc'rine t clain 9 too wherein R 1 11 and H are nothyl. 00 11. A peoticidal veopootiion aoccrdinrg to any one of' claimno to 10 whroln aid, InorganId tinpound In oPIiuji or potaooiumn inonobanie phoopbate hoxametaphoophatel; or a 20 mixture thereof.

12. A wettable powdor or doperoibie granular pooticidal compooition according to any ono of clalio 5 to 11 which comptrioev! a. from about 1Z to 9$Z by weight of the organic poeticidal compound; b. from 0.01% to 2Z by weight of the inorganic compound; *c from 0.01 to 207 by weight of wetting agent; and d, from 1% to 12% by wcight of diopornant,

13. A pooticidal componition according to any one of 30 olaimo 5 to 12 wherein caid organic compound in thiodicarb.

14. A peaticidal compoition according to claim 12 wherein said wetting agent ic an alkali metal oait of a fatty alkyl or alkenyl sulfate or oulfonato containing eight to twenty carbon atoms; an alkali metal salt o1 an alkylbonzyl or alkylnaphthyl suLfonate wherein the alkyl chain contains eight to twelve carbon atoms, an othoxylated alkyiphonol wherein the alkyl group contains eight to twelve carbon atoms; 404 4, 4r .4. 0 *l a 4r .4 S S 'i ~JI 24 a dialkylester of sodium sulfosuccinic acid wherein the dialkyl contains five to ten carbon atoms; or a polyalkylene oxide moadfied dimethylpolysiloxane in which the alkylene groups are ethylene or propylene or a mixture of both.

15. A pesticidal composition according to claim 12 whereinsaid dispersant is a starch, an alkali metal or alkaline earth salt of a lignin sulfonate, or a condensate of an alkali metal alkylnaphthalene sulfonate and an alkyl compound containing one to three carbon atoms and at least one oxygen atoms.

16. A pesticidal composition according to claim 12 which also includes an antifoaming emulsifier. 0 17. A pesticidal composition according to claim 16 r wherein said antifoaming emulsifier is a polymerized 15 dimethylsiloxane or a mixture of an alkaline earth stearate with a polyalkylene glycol ether or with a sugar-free sodium sulfonate of Kraft lignin.

18. A pesticidal composition according to claim 12 which also includes a compatibility agent.

19. A pesticidal composition according to claim 18 S.wherein said compatibility agent is a condensate of alkylene j oxide and hydrophobic base made by condensing an alkylene L oxide with an alkylene glycol wherein all alkyl substituents contain from two to four carbon atoms.

20. A pesticidal composition according to claim 19 wherein said condensate comprises ethylene oxide and a hydrophobic base made by condensing propylene oxide with propylene glycol.

21. A pesticidal composition which comprises from 70% to 95% by weight thiodicarb, from 2% to 3% by weight of sodium salt of sulfonated lauryl acid, from 8% to 15% by weight of a sulfonated naphthalene formaldehyde condensate, from 1% to 3% by weight of a dimethylpolysiloxane, and from to 1.5% by weight sodium or potassium monobasic phosphate. L 14

22. A pesticidal composition according to claim 21 which also includes a nonionic condensate of ethylene oxide and hydrophobic bases made by condensing propylene oxide with propylene glycol. 1. I C ez-= -r-b I" I i til r P f L- r C. L- i 1 1 P 1 'I I P f 11 P. R 5! 1111 r+7 DATED this day of July 1989. @0 Se S OOS@ SE S. C S. S S 555* *0 5 0 S UNION CARBIDE CORPORATION By:) 3 Regd. Patent Attorney CeO. C *5 CS 5 CC C 0*S* bCe See S CS e 0 @0 S S S. V 26 i A r -s INTERNATIONAL SEARCH REPORT International Application No PCT/US 86/00776 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) According to international Patent Classification (IPC) or to both National Classification and IPC p 4 A 01 N 47/24; A 01 N 25/22 II. FIELDS SEARCHED Minimum Documentation Searched Classification System I Classification Symbols IPC A 01 N Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched III. DOCUMENTS CONSIDERED TO ME RELEVANT' Category I Citation of Document, with Indication, where approprlate, of the relevant passages 1 I Relevant to Claim No. 3 X GB, A, 2005140 (DU PONT) 19 April 1979 see examples 4,6-8 1-21 X GB, A, 2079154 (DU PONT) 20 January 1982 see examples 3-4 1-21 X US, A, 4297370 JOBOCZENSKI) 27 October 1981 see example 3 1-21 X EP, A, 0056739 (UNION CARBIDE) 28 July 1982 see page 6, lines 19-20; page 8, 1-21 example 1 X Journal of Agricultural and Food Chemistry Svol. 27, no. 5, September/October I 1979, American Chemical Society, (Washington US) M. Chiba: "Use of Ammonium or Potassium dihydro- gen Phosphate to Protect Pesticides in Spray Mixtures Prepared with Alkaline Waters", paces 1023-1026 11-21 Special categories of cited documents: to later document published after the International filing date A d t d g te g l s o t a h i n or priority date and not in conflict with the application but document defining the general tate of the art which i not cited to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the International document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed Invention citation or other special reason (as specified) cannot be considered to involve an Inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but In the art. later than the priority date claimed document member of the same patent famlly IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this Internatnl Search Report 28th July 1986 V SEP 186 International Searching Authority Signatur ithoi Officer EUROPEAN PATENT OFFICE Sln. tu ROSSI Form PCTIISA/210 (second sheet) (January 1965) -d Pr ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL APPLICATION NO. PCT/US 86/00776 (SA 12982) This Annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 13/08/86 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document cited in search report Publication date Patent family member(s) GB-A- 2005140 19/04/79 BE-A- NL-A- FR-A,B DE-A- LU-A- JP-A- AU-A- AU-B- GB-A- 2079154 20/01/82 FR-A- AU-A- DE-A- 870790 7809781 2404398 2842281 80289 54059324 4021878 524402 2485882 7238781 3126369 Publication date 27/03/79 30/03/79 27/04/79 05/04/79 29/10/79 12/05/79 03/04/80 16/09/82 08/01/82 07/01/82 22/07/82 US-A- 4297370 27/10/81 None EP-A- 0056739 28/07/82 AU-A- 7966082 26/08/82 A 4A 't t i i Sf For more details about .this see Official Journal of the I annex European Patent Office, No. 12/82