WO1997009882A1 - Sable enduit de phosphoroamidothioate et procede correspondant - Google Patents

Sable enduit de phosphoroamidothioate et procede correspondant Download PDF

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Publication number
WO1997009882A1
WO1997009882A1 PCT/US1996/013717 US9613717W WO9709882A1 WO 1997009882 A1 WO1997009882 A1 WO 1997009882A1 US 9613717 W US9613717 W US 9613717W WO 9709882 A1 WO9709882 A1 WO 9709882A1
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WO
WIPO (PCT)
Prior art keywords
insecticidally active
composition
insecticidally
binder
present
Prior art date
Application number
PCT/US1996/013717
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English (en)
Inventor
Gary L. Cummings
A. David Lindsay
Barry A. Omilinsky
Original Assignee
Valent U.S.A. Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Valent U.S.A. Corporation filed Critical Valent U.S.A. Corporation
Priority to AU69016/96A priority Critical patent/AU6901696A/en
Publication of WO1997009882A1 publication Critical patent/WO1997009882A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A01N57/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing acyclic or cycloaliphatic radicals

Definitions

  • the present invention is directed to the achievement of chemically stable, insecticidally active phosphoroamidothioate compositions.
  • the present invention is directed to insecticidally active phosphoroamidothioate compositions based on the extremely good stability afforded by the use of sand.
  • the present invention is directed to chemically stable, insecticidally active compositions in which at least one insecticidally active phosphoroamidothioate compound has been coated on sand, and the present invention is also directed to a method for improving the chemical stability of a coated, insecticidally active composition by coating at least one insecticidally active phosphoroamidothioate compound on sand.
  • Insecticidally active compositions in various forms have been developed for diverse applications.
  • the method of preparation of the insecticidally active composition is largely determined by the physical and chemical nature of the insecticide and the intended use and method of application of the insecticide to the area to be treated.
  • phosphoroamidothioates and phosphoroamidodithioates are known in the art as having excellent insecticidal activity against a variety of insects and in a variety of environments.
  • a particularly important commercial insecticide within these classes of compounds is the insecticide acephate (generic name) or Orthene® (tradename) , which can be systemically taken up by a plant so that insects which feed and/or live on the plant are killed, in addition to those insects which directly ingest or are contacted by the insecticide.
  • Acephate and related compounds are described in U.S. Patent Nos.
  • One method of formulating technical grade phosphoroamidothioates for commercial use is to mix the technical grade powder with an anti-caking agent, such as fumed silica, and a wetting agent.
  • the wetting agent is utilized to wet the insecticide and the anti-caking agent, and the anti-caking agent is used to prevent agglomeration of the insecticide in its container.
  • This formulation of insecticide can be applied to crops as a spray solution or as a dust.
  • phosphoroamidothioates as powders allows for relatively high concentrations of insecticide to be applied to a treatment area, but the powder application suffers from various disadvantages.
  • the finely divided particles of active spray may be carried by air currents into areas where harmful effects may occur.
  • the powder has a bad odor.
  • powdered phosphoroamidothioates suffer from chemical stability problems due to hydrolytic and catalytically-driven degradation, which shortens the shelf life of the powdered insecticide.
  • pan granulation and extrusion which have been used to make granules, have adverse effects on insecticidally active phosphoroamidothioates like Orthene ® .
  • Pan granulation employs water, and the granules which are initially produced contain a significant amount of water. As a result, a dryer is used to remove the water from the granules.
  • Orthene ® degrades in water and is heat-sensitive, so the use of pan granulation is disadvantageous for producing Orthene ® formulations.
  • U.S. Patents 5,075,058 and 5,100,667 describe processes for pelletizing formulations containing insecticides such as phosphoroamidothioates.
  • U.S. Patent 5,075,058 discloses a process for forming pellets by extruding a mixture of Orthene ® , a second active ingredient, and optional components such as a limited amount of ammonium sulfate
  • U.S. Patent 5,100,667 exemplifies a process for forming pellets of Orthene® alone or in combination with a surfactant and ammonium sulfate using a pellet mill.
  • pellet mills or extruders used to form pellets from mixtures containing Orthene ® can generate heat.
  • Orthene ® is heat-sensitive, so pelletizing is disadvantageous for producing Orthene ® formulations, particularly low strength formulations.
  • an insecticidally active composition comprising particles prepared by the compaction of an admixture comprising ammonium sulfate and at least one insecticidally active phosphoroamidothioate.
  • This composition and methods for its manufacture and use are described in U.S. Patents 5,298,501, 5,352,674, and 5,369,100. As set forth in these patents, it was found that the use of ammonium sulfate in particular leads to a compacted composition which provides a high degree of chemical stability.
  • an object of the present invention is to provide chemically stable, low strength, insecticidallyactive phosphoroamidothioate formulations which are useful from a practical standpoint.
  • an object of the present invention is to provide a chemically stable, low strength, insecticidally active formulation which is based in particular on at least one insecticidally active phosphoroamidothioate rather than on any other insecticidally active compounds.
  • a characteristic feature of the present invention is the coating of at least one insecticidally active phosphoroamidothioate (rather than some other insecticidally active compound) on sand (rather than on another core material) .
  • the present inventors turned to a coating process in which Orthene ® was coated on various cores.
  • the present invention is directed to an insecticidally active composition
  • sand having coated thereon components comprising a binder and at least one insecticidally active compound of the formula:
  • R and R 1 individually are an alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms
  • R 2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl group containing 3 to 8 carbon atoms, an alkenyl group containing 2 to 18 carbon atoms or an alkynyl group containing 3 to 18 carbon atoms
  • R 3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms
  • Y is oxygen or sulfur
  • the binder is a nonaqueous, nonvolatile liquid which does not have an adverse effect on chemical stability of the composition, and wherein the at least one insecticidally active compound is present in an amount of from 0.1 to 25.0 weight percent, based on the total weight of the composition.
  • the present invention is directed to a method for improving chemical stability of a coated, insecticidally active phosphoroamidothioate composition, comprising coating sand with components comprising a binder and at least one insecticidally active compound of the formula:
  • R 1 - S R 3 wherein R and R 1 individually are an alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms, R 2 is hydrogen, an alkyl group containing l to 18 carbon atoms, a cycloalkyl group containing 3 to 8 carbon atoms, an alkenyl group containing 2 to 18 carbon atoms or an alkynyl group containing 3 to 18 carbon atoms, R 3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and Y is oxygen or sulfur, wherein the binder is a nonaqueous, nonvolatile liquid which does not have an adverse effect on chemical stability of the composition, and wherein the at least one insecticidally active compound is present in an amount of from 0.1 to 25.0 weight percent, based on the total weight of the composition.
  • phosphoroamidothioate refers to a compound or a mixture of compounds of the formula:
  • R 1 - S R 3 wherein R and R 1 individually are an alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms, R 2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl group containing 3 to 8 carbon atoms, an alkenyl group containing 2 to 18 carbon atoms or an alkynyl group containing 3 to 18 carbon atoms, R 3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and Y is oxygen or sulfur.
  • Particularly preferred compounds are those in which R and R 1 are independently a methyl, ethyl, allyl or alkenyl group; R 2 is H or an alkyl group; R 3 is hydrogen; and Y is oxygen.
  • R, R 1 , and R 2 are methyl groups, R 3 is hydrogen and Y is oxygen.
  • Compounds of the above formula may be prepared as described in U.S. Patent Nos. 3,176,600, 3,845,172 and 3,914,417, which are incorporated herein by reference in their entirety.
  • acephate (R, R 1 , R 2 are CH 3 ; R 3 is hydrogen and Y is oxygen) is commercially available from Chevron Chemical Company, San Ramon, California (e.g., Orthene ® 90S (90% acephate), Orthene ® 80S (80% acephate) and Orthene ® 75S (75% acephate) ) .
  • insecticidally active component in the formulation of this invention forms the insecticidally active component in the formulation of this invention.
  • the amount of insecticidally active component in the invention formulation can be from about 0.1 to about 25.0 weight percent, based on the total weight of the composition.
  • the insecticidally active component is present in an amount of from about 0.1 to about 10.0 weight percent, and more preferably, the insecticidally active component is present in an amount of from about 0.5 to about 5.0 weight percent. In a particularly preferred embodiment, the insecticidally active component is present in an amount of about 2.5 weight percent.
  • An important feature of the present invention is the discovery that for coated formulations which contain an insecticidally active phosphoroamidothioate, the insecticidally active phosphoroamidothioate should be coated on sand, rather than on some other core material, in order to achieve good chemical stability. If the sand is replaced with a seemingly similar material (e.g., granules of ammonium sulfate, which is usually considered to be an inert, non-porous material) , the chemical stability of the formulation is adversely affected.
  • a seemingly similar material e.g., granules of ammonium sulfate, which is usually considered to be an inert, non-porous material
  • sand is used for the core of the present invention.
  • Sand is a mineralogically defined form of silicon dioxide and specifically is a gritty or particulate form of the chemical.
  • sand particles can be quite angular and rough and can have sharp edges, like a diamond, or they can be rather smooth, almost spherical, like ball bearings.
  • the particles that are relatively smooth are referred to as subangular. It is preferred for the sand to be subangular in the present invention so that the coating can be built up and so that there are no sharp edges to peel off the coating.
  • the sand particle size can be selected from a wide range of sizes. Typical sizes include: U.S. Mesh Diameter
  • the insecticidally active phosphoroamidothioate adheres to the sand core via a binder. That is, the sand core is coated with a binder, and the insecticidally active phosphoroamidothioate adheres to the binder-coated sand core. It should be noted that the process can be initiated by mixing the insecticidally active phosphoroamidothioate and the sand and then adding the binder.
  • the binder can be any nonaqueous, nonvolatile liquid which does not adversely affect the chemical stability of the insecticidally active composition.
  • a key feature of the binder is that it is a material which is nonvolatile, thereby allowing a continuous film coating to be formed without the use of heat or any chemical reaction.
  • the insecticidally active component is not soluble in the binder.
  • binders include refined soybean oil, refined cottonseed oil, refined corn oil, peanut oil, diethylene glycol, isopropylbiphenyl (e.g., Sure Sol-330, manufactured by Koch Chemical Company, Corpus Christi, Texas) , alkylphenyl polyether alcohol (e.g., Enviromark 3, manufactured by Formulogics, Inc., Trenton, New Jersey) , propylene glycol, d-limonene (d-p-mentha-1, 8 diene) , mineral oils (e.g., Klearol and Blandol, manufactured by Witco Chemical Corp.
  • N-methylpyrrolidone is an example of a binder which is not suitable for the present invention, because it has an adverse effect on the chemical stability of the composition, as can be seen from the experimentation set forth subsequently.
  • Other binders which should not be used are water-soluble binders and heat-setting binders, because of the deleterious impact of water and/or heat on the chemical stability.
  • the amount of binder which is used can range from about 0.1 to about 15.0 weight percent, based on the total weight of the composition.
  • the binder is present in an amount of from about 0.1 to about 10.0 weight percent, and more preferably, the binder is present in an amount of from about 0.5 to about 5.0 weight percent. In a particularly preferred embodiment, the binder is present in an amount of from about 0.5 to about 2.0 weight percent.
  • a drying agent can be added to the formulation to obtain dry, free-flowing granules.
  • Suitable drying agents can be selected from classes of finely divided carriers which do not adversely affect the chemical stability of the insecticidally active phosphoroamidothioate.
  • Suitable drying agents include, by way of example, hydrated silica and other highly absorptive silicas, such as fumed silica, although it should be noted that drying agents other than silica-based drying agents can also be used.
  • the drying agent can be present in an amount of up to about 6 weight percent, preferably up to about 5 weight percent, based on the total weight of the composition.
  • additives can be included in the composition as desired in suitable amounts.
  • other additives can be reodorants, bittering agents, colorants, and other finely divided carriers.
  • rhodamine dye can be included in the composition. It is important that additive or additives used do not adversely affect the chemical stability of the insecticidally active phosphoroamidothioate.
  • other pesticides can be added in suitable amounts.
  • a nonvolatile liquid pesticide may even be used as the binder, if chemically compatible. It is important that additional pesticide or pesticides used do not adversely affect the chemical stability of the insecticidally active phosphoroamidothioate.
  • no active ingredients are present other than the insecticidally active phosphoroamidothioate active ingredien .
  • composition of the present invention can be made as follows. First, sand and a binder are placed in a mixer (e.g., a Continental mixer), and the mixer is operated so that the sand is uniformly coated with the binder. Then, the insecticidally active phosphoroamidothioate is added to the mixer, and the mixer is operated so that the insecticidally active phosphoroamidothioate uniformly adheres to the binder- coated sand. If the granules are too damp, a drying agent can be added to provide a dry, free-flowing granular product.
  • a mixer e.g., a Continental mixer
  • the process can be initiated by mixing the insecticidally active phosphoroamidothioate and the sand and then adding the binder.
  • An insecticidally active composition made in accordance with the present invention has very good chemical stability.
  • Very good chemical stability can be considered as meaning that the amount of the insecticidally active phosphoroamidothioates in the formulation does not diminish by more than about 10% when stored under accelerated storage conditions of 28 days at 50-55°C as compared to the amount of the phosphoroamidothioates in the formulation at the time of preparation.
  • insecticidally active phosphoroamidothioate particles which do not experience more than about a 10% decrease in the amount of the phosphoroamidothioate evidence the fact that such particles will possess very good long term storage stability under ambient conditions.
  • the 10% degradation maximum is a minimally acceptable target for defining shelf life and that much less degradation is highly preferable.
  • the particles are useful in a method for controlling insects by application of the particles onto the insects' habitat.
  • the particles can be applied onto the habitat in an amount sufficient to provide acceptable control of the insects.
  • the particles are applied at a rate of at least about 0.5 lb (0.227 kg) acephate per acre and more preferably at a rate of from about 0.5 lb (0.227 kg) to about 2.0 lbs (0.909 kg) acephate per acre (0.004 square kilometer) .
  • the amount of particles to be applied per acre (0.004 square kilometer) will depend upon the concentration of acephate in the particles.
  • particles containing 5% acephate will need to be applied at 10 lbs (2.27 kg) per acre (0.004 square kilometer) to achieve a dosage of 0.5 lb (0.227 kg) acephate per acre (0.004 square kilometer) .
  • the following examples illustrate specific embodiments of the invention but should not be construed as limiting the scope of the claims in any way. All parts, percents, ratios and the like are by weight unless otherwise indicated.
  • the purpose of this example is to investigate the chemical stability of insecticidally active phosphoroamidothioate embodiments having a sand core, particularly with the use of various binders.
  • Granules of sand were added to a jar, and then a liquid binder as set forth below in Tables 1-3 was added. The jar was tumbled/shaken to uniformly coat/treat the granules. De-lumped Orthene ® Tech (which contains 97-99% acephate) was then added, and the jar was tumbled/shaken to adhere the Orthene ® to the binder-coated granules. In addition, Hi-Sil 532ED or Hi-Sil 233 (hydrated silica) was added to achieve a dry, free-flowing granular. The amount of each component which was used is shown in Tables 1-3 below. The samples were placed into glass jars which were sealed for aging. /09882 PC17US96/13717
  • the samples were analyzed to provide an initial active ingredient concentration (which was obtained by assaying a sample following one month aging in a freezer at -20°F ( samples do not degrade measurably at this temperature ) ) and active ingredient concentrations after various time periods and at temperatures to determine the amount of active ingredient degradation and thereby evaluate the chemical stability of the compositions.
  • the results are shown below in Tables 1-3.
  • Cottonseed Oil 1.2 1.2 X X X X X X X X X X
  • Aromatic 200 X X X X X X X X 1.2
  • the purpose of this example is to demonstrate the poor chemical stability which was obtained when ammonium sulfate was used as the core in the coated, insecticidally active phosporoamidothioate composition instead of using sand. As noted above, this result was surprising in view of the very good chemical stability which was obtained with the use of ammonium sulfate in compacted particles.
  • Granules of ammonium sulfate were added to a jar. Then, a liquid binder as set forth below in Table 4 was added, and the jar was tumbled/shaken to uniformly coat the granules. De-lumped Orthene ® Tech was then added, and the jar was tumbled/shaken to adhere the Orthene ® to the binder-coated granules. Where the granules were too damp, Hi-Sil 233 was added to achieve a dry, free-flowing granular. The amount of each component which was used is shown below in Table 4. The samples were placed into glass jars which were sealed for aging.
  • the samples were analyzed to provide an initial active ingredient concentration (which was obtained by assaying a sample following one month aging in a freezer at -20°F) and active ingredient concentrations after various time periods and temperatures to determine the amount of active ingredient degradation and thereby evaluate the chemical stability of the compositions.
  • the results are shown below in Table 4.
  • Cottonseed Oil 1.0 1.7 X X X X X X X X X X
  • Aromatic 200 X X X X X X X X X 1.8 X d-limonene X X X X X X X X X 1.7
  • the purpose of this example is to further demonstrate the significance of employing sand, rather than another conventionally-used material, as the core in the coated, insecticidally active composition. It is noted that in this example, the sand-based embodiments had a higher insecticidally active phosphoroamidothioate amount than in Example 1, thereby demonstrating the unexpected superiority of present invention over the recited range of insecticidally active phosphoroamidothioate content.
  • Granules of either Biodac (a cellulosic-based granule) or sand were added to a jar, and then the liquid binder (in this case, refined soybean oil) was added. The jar was tumbled/shaken to uniformly coa /treat the granules.
  • Orthene ® 90S which contains 90% acephate, with the remainder being inerts such as silica and surfactant was then added, and the jar was tumbled/shaken to uniformly adhere the Orthene ® to the binder-coated granules. Where the granules were too damp, Hi-Sil 233 was added to achieve a dry, free-flowing granular.
  • Rhodamine dye was added in a similar manner to the addition of the Orthene ® 90S.
  • the amount of each component which was used is shown in Table 5 below.
  • the samples were placed into glass jars which were sealed for aging. With respect to the sand-based samples, Sample FF was bottled as produced and had lumps consisting of agglomerates of the sand, binder and Orthene ® 90S present rather than individual particles, while Sample GG was screened prior to bottling and thus was expected to be more uniform.
  • the samples were analyzed to provide an initial active ingredient concentration (which was obtained by assaying a sample following one month aging in a freezer at -20°F) and active ingredient concentrations after one month of aging at temperatures of 18°C, 33°C and 44°C to determine the amount of active ingredient degradation and thereby evaluate the chemical stability of the compositions.
  • the results are shown below in Table 5.
  • the sample based on a Biodac core suffered from significant degradation, while the samples based on a sand core did not experience significant degradation (the increase in active ingredient concentration in Sample FF might be attributed to the non-uniformity of the sample due to lack of screening) .
  • the sand-based insecticidally active phosphoroamidothioate compositions provided very good chemical stability as compared with the Biodac-based insecticidally active phosphoroamidothioate composition.
  • the purpose of this example is to further demonstrate that insecticidally active phosphoroamidothioate compositions containing the conventionally-used material Biodac as the core do not have good chemical stability.
  • the data set forth above show that unexpectedly superior chemical stability can be obtained when an insecticidally' active phosphoroamidothioate is coated on sand rather than on another material, particularly where the binder which is used to adhere the insecticidally active phosphoroamidothioate to the sand is a binder which itself does not adversely affect the chemical stability of the insecticidally active phosphoroamidothioate.
  • insecticidally active composition of the present invention is chemically stable, use of this composition in methods for controlling insects will provide very good results as compared with compositions used previously, because a smaller amount of insecticidally active phosphoroamidothioate will degrade over time.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne une composition chimiquement stable et active en tant qu'insecticide, comprenant du sable enduit d'un liant et de 0,1 à 25,0 % en poids, sur la base du poids total de la composition, d'au moins un phosphoroamidothioate actif en tant qu'insecticide. Le liant est un liquide compatible, non aqueux et non volatil. Un procédé d'amélioration de la stabilité chimique d'une composition de phosphoroamidothioate enduisant un support, active en tant qu'insecticide, comprend l'application sur du sable d'au moins une composition de phosphoroamidothioate active en tant qu'insecticide.
PCT/US1996/013717 1995-09-14 1996-08-30 Sable enduit de phosphoroamidothioate et procede correspondant WO1997009882A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU69016/96A AU6901696A (en) 1995-09-14 1996-08-30 Phosphoroamidothioate coated sand and method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US52798295A 1995-09-14 1995-09-14
US08/527,982 1995-09-14

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008061425A1 (de) 2007-12-11 2009-06-18 Sumitomo Chemical Co., Ltd. Olefinpolymerisationsreaktor, Polyolefinherstellungssystem und Polyolefinherstellungsverfahren
WO2014055208A3 (fr) * 2012-10-05 2014-06-26 Agrofresh Inc. Formulations d'huile comprenant des épaississants
US9012515B2 (en) 2007-08-03 2015-04-21 Rohm And Haas Company Oil formulations with thickeners

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3716600A (en) * 1970-02-24 1973-02-13 Chevron Res N-acyl derivatives of phosphoroamidothioates
US3845172A (en) * 1971-05-28 1974-10-29 Chevron Res N-hydrocarboyl phosphoroamido-thioates and phosphoroamidodithioates
US4855309A (en) * 1985-12-21 1989-08-08 Hoechst Aktiengesellschaft Pyridine derivatives, agents containing same, and the use thereof as pesticides
US4954529A (en) * 1987-12-04 1990-09-04 Hoechst Aktiengesellschaft (Thio)benzoylureas and functional derivatives thereof, processes for their preparation, agents containing them and their use as agents for combating pests
US5169644A (en) * 1985-02-16 1992-12-08 Bayer Aktiengesellschaft Combination carrier granules
US5326573A (en) * 1989-01-18 1994-07-05 Bayer Aktiengesellschaft Coated granules containing liquid and solid active compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3716600A (en) * 1970-02-24 1973-02-13 Chevron Res N-acyl derivatives of phosphoroamidothioates
US3845172A (en) * 1971-05-28 1974-10-29 Chevron Res N-hydrocarboyl phosphoroamido-thioates and phosphoroamidodithioates
US5169644A (en) * 1985-02-16 1992-12-08 Bayer Aktiengesellschaft Combination carrier granules
US4855309A (en) * 1985-12-21 1989-08-08 Hoechst Aktiengesellschaft Pyridine derivatives, agents containing same, and the use thereof as pesticides
US4954529A (en) * 1987-12-04 1990-09-04 Hoechst Aktiengesellschaft (Thio)benzoylureas and functional derivatives thereof, processes for their preparation, agents containing them and their use as agents for combating pests
US5326573A (en) * 1989-01-18 1994-07-05 Bayer Aktiengesellschaft Coated granules containing liquid and solid active compounds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9012515B2 (en) 2007-08-03 2015-04-21 Rohm And Haas Company Oil formulations with thickeners
US9282736B2 (en) 2007-08-03 2016-03-15 Agrofresh Inc. Oil formulations with thickeners
DE102008061425A1 (de) 2007-12-11 2009-06-18 Sumitomo Chemical Co., Ltd. Olefinpolymerisationsreaktor, Polyolefinherstellungssystem und Polyolefinherstellungsverfahren
WO2014055208A3 (fr) * 2012-10-05 2014-06-26 Agrofresh Inc. Formulations d'huile comprenant des épaississants

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