CA2093737A1 - Fungicidal compositions and methods for production thereof - Google Patents
Fungicidal compositions and methods for production thereofInfo
- Publication number
- CA2093737A1 CA2093737A1 CA002093737A CA2093737A CA2093737A1 CA 2093737 A1 CA2093737 A1 CA 2093737A1 CA 002093737 A CA002093737 A CA 002093737A CA 2093737 A CA2093737 A CA 2093737A CA 2093737 A1 CA2093737 A1 CA 2093737A1
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- moisture content
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
- A01N47/14—Di-thio analogues thereof
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/26—Oxidation products of dithiocarbamic acid derivatives, e.g. thiuram sulfides
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Novel and improved fungicidal dithiocarbamate particulate compositions comprising one or more components selected from dithiocarbamates and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly enhance the flowability of the particulate composition, reduce the dustiness of thc composition, increase the bulk density of the composition and/or reduce the ethylenethiourea content of the composition. Methods for producing such particulate compositions are presented wherein controlled slurry production and spray-drying are effective in producing such compositions.
Novel and improved fungicidal dithiocarbamate particulate compositions comprising one or more components selected from dithiocarbamates and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly enhance the flowability of the particulate composition, reduce the dustiness of thc composition, increase the bulk density of the composition and/or reduce the ethylenethiourea content of the composition. Methods for producing such particulate compositions are presented wherein controlled slurry production and spray-drying are effective in producing such compositions.
Description
209373~
BACKGROUND
Fungicidal dithiocarbamate and bisdithiocarbamoyl disulfide compounds have utility when contained in particulate compositions as powders or granules. Such powders or granules often are dispersed, dissolved or otherwise mixed into liquids to form slurries or other mixtures for use in agricultural sprays. Such mixtures are frequently made at the site of application after prior storage of the particulate compositions.
The storage, handling, dispersing and applying of such dithiocarbamate and bisdithiocarbamoyl disulfide compositions can have attending complications and problems. Such problems can require the us~ of stabilizing agents to prevent degradation during storage; costly binders or production methods to reduce attrition and undersizing of particles leading to dustiness and product loss; dispersing, wetting and surfacting agents; and mechanical methods to assist in formulating and handling spray mixtures. Also desirecl is the minimization of undesirable by-products, for example ethylenethiourea (ETU), created during these activities. There continues to be a need for fungicidal dithiocarbamate and bisdithiocarbamoyl disulfide compositions with improved characteris~ics as well as for methods of producing such compositions.
~UMMA~Y OF THE INVEMION
Novel and improved fungicidal dithiocarbamate and bisdithiocarbamoyldisulfide particulate compositions are embodied in this specification. Such compositions comprise a fungicidally effective amount ~Q93737 of one or more components selected from dithiocarbamate~ and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly enhance the flowability of the particulate composition, reduce the dustiness of the composition, increase the bulk density of the cornposition and/or reduce the ethylenethiourea content of the composition.
Methods for producing such dithiocarbamate and bisdithiocarbamoyldisulfide particulate compositions are presented wherein controlled slurry production and spray-drying are effective in producing such compositions with enhanced properties. Such methods are novel and provide economical benefits in addition to the enhanced characteristics of the produced compositions.
FIGURES
Figure 1 depicts two particle size distribution charts for a Sample A
(low moisture compositions) and Sample B (controlled moisture compositions) DESC:RIPTIONS OF THE PREFERRED EMBODIMENI$
C~OMe~2SITION$
One embodiment of the present invention is a particulate composition comprising a fungicidally effective amount of one or more components selected from dithiocarbamates and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly enhance flowability of said particulate composition. More preferably, the amount of moisture content is optionally effective to reduce the dustiness of the compos~tion, ~0937~7 Increase the bulk density of the composition and/or reduce the ethylenethiourea content of the composi~ion when ethylenethiourea is a producible product of compounds present in the composition.
Preferably, the one or more dithiacarbamate(s) of the embodied composition is selected from ethylenebisdithiocarbamate metal salts, dimethyldithiocarbamate metal salts, and propylenebisdithiocarbamate metal salts. Preferred ethylenebisdithiocarbamate metal salts are mancozeb ~a coordination product of zinc and manganese ethylene bisdithiocarbamate}, maneb ~manganese ethylenebisdithiocarbamate} and zineb {zinc ethylene-bisdithiocarbamate~. A preferred dimethyldithiocarbamate metal salt is ziram ~zinc dimethyldithiocarbamate}. A preferred propylene-bisdithiocarbamate metal salt is propineb {[[(1-methyl-1,2-ethanediyl) bis[carbamatothioato]](2-)]zinc homopolymer}. Another preferred dithiocarbamate is metiram {tris[amine-[ethylene bis(dithiocarbamato)]zinc(ll)][tetrahydro-1 ,2,4,7-dithiadia-zocine-3,8-dithione] polymer~. A preferred bisdithiocarbamoyl disulfide is thiram {bis~dimethylthiocarbamoyl)disulfide}. These preferred metal salt(s) and bisdithiocarbamoyl disulfide may be present singularly or in combinations.
Preferably, the total weight of the components selected from dithiocarbamates and bisdithiocarbamoyl disulfides is from about 20 to about 95 weight percent of the embodied particulate compositions; more preferably, at least about 50 % by weight; and even more preferably, at least about 80 % by weight.
The moisture content of embodied compositions has unexpectedly provided valued benefits. The moisture content can be a wide variety of material in liquid or vapor form and in a chemically bonded, hydrated or unhydrated state. In one preferred embodiment, the moisture is comprised 20~3737 of one or more component(s) selected from water, alcohol, ammor~ia, carbon disulfide and glycol. More preferably, the moisture content is predominantly water. The moisture content is preferàbly from about 2.5 to about 20 % of the embodied particulate compositions by weight, more preferably about 2.5 to about 10 % of the embodied particulate compositions by weight. In one preferred embodiment the moisture content i~ predominantly water of hydration.
Embodied compositions can have significantly enhanced flowability relative to compositions not having moisture content from about 2.5 to about 20 % by weight of the embodied particulate compositions. Preferably the flowability of embodied compositions is such that the angle of repose for such compositions is less than about sixty degrees from the horizontal.
Embodied compositions after production can have an initial ethylenethiourea content of less than about 0.1 weight percent of the total composition weight. One preferred embodiment is a composition wherein the dithiocarbamate comprises mancozeb and the initial ethylen~thiourea content is from about 0.01 to about 0.05 weight percent of the total composition weight. More preferably, the ethylenethiourea content of the particulate composition maintained at a temperature of about 54 C for two weeks after production of the composition is less than about 0.3 weight percent, more preferably from about 0.10 to about 0.25 weight percent, even more preferably less than about 0.20 weight percent of the total composition weight. Another embodied composition maintained at a temperature of about 54 C for four weeks after production of the composition has an ethylenethiourea content of less than about 0.3 weight percent, more preferably less than about 0.15 weight percent of the total composition weight.
20937~7 Embodied compositions preferably have a bulk density of at least about 0.5 gram per cubic centimeter, more preferably at least about 0.75 gram per cubic centimeter, even more preferably from about 0.75 to about 1.0 gram per cubic centimeter.
Embodied compositions preferably have a dry particle median size range of from about 20 to about 400 micrometers (~m)~ Preferably, the particle size and distribution is such that the emboclied composition has a significantly reduced dustiness, that is, reduced volume of particles with particle diameters less than about 5 microrneters, more perferably less than about 10 micrometers, such that at least about 50 per cent by volume of the particles have a diameter greater than 5 micrometers, more preferably 10 micrometers. In one embodiment the volume percent amount o~ dry particles less than about 15 micrometers is at most about 50 percent of the volume percent amount of dry particles present when the composition is dried to 1 percent moisture content. More preferably, the volume percent amount of dry particles less than 15 micrometers is at most about 25 percent of the volume percent amount of dry particles present when said composition is dried to 1 percent moisture content. Also in some preferred embodiments the volume percent amount of dry particles greater than about 20 micrometers is at least about 50 percent of the volume percent amount of dry particles present when said composition is dried to 1 percent moisture content.
A preferred embodiment is a composition comprising (a) particles comprising one or more components selected from ethylenebisdithiocarbamate metal salts, dimethyldithiocarbamate metal salts, propylenedithiocarbamate metal salts, metiram and thiram, and (b) water; wherein the total weight of said components is from about 20 to about 90 weight per cent of said composition and wherein said composition has a bulk density of at least about 0.5 gram per cubic centimeter and the character of an angle of repose of at most about sixty degrees and wherein at least about fifty per cent by volume of said particles as dry particle have a diameter greater than five micrometers.
MEll '~DI~
Other embodiments of the present inventions include m~thods for the production of the embodied compositions. One embodied method is a method for producing a particulate composition comprising from about 20 to about 95 weight percent of the embodied particulate compositions of components selected from dithiocarbamates and bisdithiocarbamoyl disulfides, said method comprising (1) creating a slurry comprising particles of said components selected from dithiocarbamates and bisdithiocarbamoyl disulfides, said particles having a median particle size of from about 2 to about 7 micrometers; and (2) spray-drying said slurry to produce said particulate composition with a moisture content of from about ~ to about 10 weight percent of the embodied particulate compositions;
said creating and spray-drying being effective to significantly enhance the flowability of said particulate composition.
One preferred embodiment is the method ~Nherein said dithiocarbamate is mancozeb. In such method in the slurry said particles preferably can have a median particle size of from about 3 to about 6 micrometers.
Another embodied method is a method for producing a particulate composition havin~ enhanced flowability and comprising from about 50 to about 9~ weight percent of the embodiecl particulate compositions of components selected from dithiocarbamates and bisdithiocarbarrloyl disulfides, said method comprising (1) producing a ~irst slurry comprising (a) particles of said components selected frorn dithiocarbamates (preferably manganese dithiocarbamate) and bisdithiocarbamoyl disulfides, preferably in a weight percent of at least about ten percent of the weight of the slurry, (b) one or more water soluble zinc salt(s), preferably zinc chloride and/or zinc sulphate, and (c) water;
(2) wet-milling said first slurry to produce a second slurry h&ving a median particle size of about 2 to about 7 micrometers; and (3) spray-drying said second slurry to produce said particulate composition with a moisture content of about 2 to about 10 weight percent of the embodied particulate composition.
In one preferred method the first slurry comprises (a) at least ten (1.0) weight percent of a wet cake of maneb;
(b) manganese ions and zinc ions in a respecti~,e mol~ ratio of about ten to one; and (c) at least about forty t40) weight percent of water.
Even more preferably, the first slurry has at least about fifty (50) weight percent of a wet cake of maneb and the second slurry has a median particle size of about 5 micrometers.
In further embodiments, the first slurry composition further comprises 20937~7 at least about 2 weight percent of one or more additive(s) solected from stabilizing agents, dispersing agents, anti-foam agents, wetting agents, binding agents, filler agents and extending agents.
The following experiments illustrate embodiments of the present invention but are not intended to limit the scope thereof.
Experiment 1 -~rod~ Q~of Dithioca~am~Q~L~j~
Formulation of nine dithiocarbamate slurries was performed by admixing components to create each slurry with about the following composition:
ComponentWeight percent Wet Cake (about 60% Mn EBDC~) 72.07 Dispersant~ 2.60 Antifoam agent 0.02 Hexamethylenetetramine Stabilizer 1.42 ZnSO4 7H20 4.85 Water 1 9.04 "Mn EBDC" - manganese ethylenebisdithiocarbamat~
~ The production for each slurry was the same except that the slurries for samples 1-D, 1-W, 2-W, 3-W and 4-W had WafexrM dispersant as the dispersant and the slurries for samples 1-R, 2-R, 3-R and 4-R had Reax 100M~ dispersant as the dispersant.
After creation, each slurries were then wet-milled to a median particle size of about five (5) micn~meters.
~perimçnt ? - Production of Sam~le 1-p ~om~Qn ~93737 The slurry for Sample l-D from experiment 1 was spray dried with an inlet temperature of about 320-33~oC and an outlet temperature of about 80C to produce an intermediate composition which was subjected to a second drying stage to produce Sample 1-D.
Experiment 3 - PrnductiQn_of Sa..mple 1-W ~-W. 3-W~4-W. 1-R, 2-R. 3-R and 4-R ComDositiQns The procedure from experiment 1 was usod to produce eight (8) slurry samples, e.g., 1-W, 2-W, 3-W, and 4-W for the first set and 1-R, 2-R, 3-R, and 4-R for the second set. The eight slurry samples were th~n treated to a single spray-drying without a second drying stage. The respective spray drying conditions were an inlet temperature of 320-330C and the following outlet temperatures:
Samples Outlet Temperature 1 -W, 1 -R 11 5C
2-W, 2-R 1 00C
3-W, 3-R 90C
4-W, 4-R 70C
~937~7 Takle !
Initial Proper~ies Sample H2O Particle Size~ m ) ETU~
No. (%)~ _ _ 50%~ 20%~ (%)~
1-D 0.9 6.0 12.5 0.12 1-W 3.3 5.9 17.8 0.13 1 - R 4.0 6.4 17.3 0.13 2-R 6.8 6.3 17.9 0.12 2-W 7.0 5.6 17.2 0.097 3-R 9.8 7.2 18.9 0.071 3-W 10.3 6.2 18.0 0.087 4-R 12.0 14.9 48.6 0.057 4-W 13.1 14.9 43.1 0.024 After 2 weeks at 54C
Sampie H20 Particle Size (~m ) ETU
No. (%! 50% 90% ~ (%) 1 - D 0.79 6.0 12.4 0.28 1-W 2.7 7.2 22.7 0.22 1 - R 2.7 5.5 16.2 0.24 2-W 6.8 6.4 19.8 0.20 2-R 6.8 7.9 23.6 0.16 3-R 9.1 9.7 26.9 0.15 3-W 9.4 8.0 23.3 0.17 4-R 10.1 41.6 77.5 0.10 4-W 10.3 27.1 61.9 0.11 2~93~37 After 4 weeks at 54C
Sample H20 Particle Size(llm ) ETU
No. (%) . 50% 90% (/Q~
1-D 0.80 6~5 13.3 0.20 1-W 2.8 11.5 31.6 0.14 1-R 3.2 8.5 27.3 0.14 2-W 7.3 9.~ 2~.6 0.~2 2-R 7.1 1~.9 35.6 0.082 3-R 10.1 13.1 37.5 0.089 3-W 10.2 16.1 39.1 0.06B
4-R 11.1 30.8 51.1 0.023 4-W 10.5 40.9 73.2 O.û11 ~For the entire Table I all H2O and ETU "%" are by weight and all Particle Size "%" are by volume.
After redispersion in H2O.
ETU is ethylenethiourea Experiment 4 - Dry Particle Size Analysis Particle size analysis was performed to compare the particle size distribution in a low moisture dithiocarbamate composition (Sample A, same as 1-D hereinabove) and a relatively higher moisture dithiocarbamate composition (Sample B, prepared substantially same but with higher water content). The samples had the following characteristics:
~37~
TablÇ ll ~ampl~ A E~
~0 <1% 3.7%
Median Particle Size 5.9 ~m 29.9 ~m Particle Size Distribution 10% < 0.8 ~m < 7.1 ,um 50% S 5.9 ~lm s 29.9 ~Lm 75% S 10.4 ~lm S 42.7 llm 90% s 14.9 ~lm s 55.0 ~m The distribution is charted in Figure 1, which illustrates a significantly different distribution of particle diameters. Dry particle size analysis of other samples were performed with the following rasults.
20~373~
T~ble ILI
$amp!e ~ MediaQ~
1-D ~1 5.9 The following comparison of bulk densities were determined:
Table IV
~am~le HzOt%! BuLk ~nsity (g 1-D 0.98 0.45 2-W 7.0 0.71
BACKGROUND
Fungicidal dithiocarbamate and bisdithiocarbamoyl disulfide compounds have utility when contained in particulate compositions as powders or granules. Such powders or granules often are dispersed, dissolved or otherwise mixed into liquids to form slurries or other mixtures for use in agricultural sprays. Such mixtures are frequently made at the site of application after prior storage of the particulate compositions.
The storage, handling, dispersing and applying of such dithiocarbamate and bisdithiocarbamoyl disulfide compositions can have attending complications and problems. Such problems can require the us~ of stabilizing agents to prevent degradation during storage; costly binders or production methods to reduce attrition and undersizing of particles leading to dustiness and product loss; dispersing, wetting and surfacting agents; and mechanical methods to assist in formulating and handling spray mixtures. Also desirecl is the minimization of undesirable by-products, for example ethylenethiourea (ETU), created during these activities. There continues to be a need for fungicidal dithiocarbamate and bisdithiocarbamoyl disulfide compositions with improved characteris~ics as well as for methods of producing such compositions.
~UMMA~Y OF THE INVEMION
Novel and improved fungicidal dithiocarbamate and bisdithiocarbamoyldisulfide particulate compositions are embodied in this specification. Such compositions comprise a fungicidally effective amount ~Q93737 of one or more components selected from dithiocarbamate~ and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly enhance the flowability of the particulate composition, reduce the dustiness of the composition, increase the bulk density of the cornposition and/or reduce the ethylenethiourea content of the composition.
Methods for producing such dithiocarbamate and bisdithiocarbamoyldisulfide particulate compositions are presented wherein controlled slurry production and spray-drying are effective in producing such compositions with enhanced properties. Such methods are novel and provide economical benefits in addition to the enhanced characteristics of the produced compositions.
FIGURES
Figure 1 depicts two particle size distribution charts for a Sample A
(low moisture compositions) and Sample B (controlled moisture compositions) DESC:RIPTIONS OF THE PREFERRED EMBODIMENI$
C~OMe~2SITION$
One embodiment of the present invention is a particulate composition comprising a fungicidally effective amount of one or more components selected from dithiocarbamates and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly enhance flowability of said particulate composition. More preferably, the amount of moisture content is optionally effective to reduce the dustiness of the compos~tion, ~0937~7 Increase the bulk density of the composition and/or reduce the ethylenethiourea content of the composi~ion when ethylenethiourea is a producible product of compounds present in the composition.
Preferably, the one or more dithiacarbamate(s) of the embodied composition is selected from ethylenebisdithiocarbamate metal salts, dimethyldithiocarbamate metal salts, and propylenebisdithiocarbamate metal salts. Preferred ethylenebisdithiocarbamate metal salts are mancozeb ~a coordination product of zinc and manganese ethylene bisdithiocarbamate}, maneb ~manganese ethylenebisdithiocarbamate} and zineb {zinc ethylene-bisdithiocarbamate~. A preferred dimethyldithiocarbamate metal salt is ziram ~zinc dimethyldithiocarbamate}. A preferred propylene-bisdithiocarbamate metal salt is propineb {[[(1-methyl-1,2-ethanediyl) bis[carbamatothioato]](2-)]zinc homopolymer}. Another preferred dithiocarbamate is metiram {tris[amine-[ethylene bis(dithiocarbamato)]zinc(ll)][tetrahydro-1 ,2,4,7-dithiadia-zocine-3,8-dithione] polymer~. A preferred bisdithiocarbamoyl disulfide is thiram {bis~dimethylthiocarbamoyl)disulfide}. These preferred metal salt(s) and bisdithiocarbamoyl disulfide may be present singularly or in combinations.
Preferably, the total weight of the components selected from dithiocarbamates and bisdithiocarbamoyl disulfides is from about 20 to about 95 weight percent of the embodied particulate compositions; more preferably, at least about 50 % by weight; and even more preferably, at least about 80 % by weight.
The moisture content of embodied compositions has unexpectedly provided valued benefits. The moisture content can be a wide variety of material in liquid or vapor form and in a chemically bonded, hydrated or unhydrated state. In one preferred embodiment, the moisture is comprised 20~3737 of one or more component(s) selected from water, alcohol, ammor~ia, carbon disulfide and glycol. More preferably, the moisture content is predominantly water. The moisture content is preferàbly from about 2.5 to about 20 % of the embodied particulate compositions by weight, more preferably about 2.5 to about 10 % of the embodied particulate compositions by weight. In one preferred embodiment the moisture content i~ predominantly water of hydration.
Embodied compositions can have significantly enhanced flowability relative to compositions not having moisture content from about 2.5 to about 20 % by weight of the embodied particulate compositions. Preferably the flowability of embodied compositions is such that the angle of repose for such compositions is less than about sixty degrees from the horizontal.
Embodied compositions after production can have an initial ethylenethiourea content of less than about 0.1 weight percent of the total composition weight. One preferred embodiment is a composition wherein the dithiocarbamate comprises mancozeb and the initial ethylen~thiourea content is from about 0.01 to about 0.05 weight percent of the total composition weight. More preferably, the ethylenethiourea content of the particulate composition maintained at a temperature of about 54 C for two weeks after production of the composition is less than about 0.3 weight percent, more preferably from about 0.10 to about 0.25 weight percent, even more preferably less than about 0.20 weight percent of the total composition weight. Another embodied composition maintained at a temperature of about 54 C for four weeks after production of the composition has an ethylenethiourea content of less than about 0.3 weight percent, more preferably less than about 0.15 weight percent of the total composition weight.
20937~7 Embodied compositions preferably have a bulk density of at least about 0.5 gram per cubic centimeter, more preferably at least about 0.75 gram per cubic centimeter, even more preferably from about 0.75 to about 1.0 gram per cubic centimeter.
Embodied compositions preferably have a dry particle median size range of from about 20 to about 400 micrometers (~m)~ Preferably, the particle size and distribution is such that the emboclied composition has a significantly reduced dustiness, that is, reduced volume of particles with particle diameters less than about 5 microrneters, more perferably less than about 10 micrometers, such that at least about 50 per cent by volume of the particles have a diameter greater than 5 micrometers, more preferably 10 micrometers. In one embodiment the volume percent amount o~ dry particles less than about 15 micrometers is at most about 50 percent of the volume percent amount of dry particles present when the composition is dried to 1 percent moisture content. More preferably, the volume percent amount of dry particles less than 15 micrometers is at most about 25 percent of the volume percent amount of dry particles present when said composition is dried to 1 percent moisture content. Also in some preferred embodiments the volume percent amount of dry particles greater than about 20 micrometers is at least about 50 percent of the volume percent amount of dry particles present when said composition is dried to 1 percent moisture content.
A preferred embodiment is a composition comprising (a) particles comprising one or more components selected from ethylenebisdithiocarbamate metal salts, dimethyldithiocarbamate metal salts, propylenedithiocarbamate metal salts, metiram and thiram, and (b) water; wherein the total weight of said components is from about 20 to about 90 weight per cent of said composition and wherein said composition has a bulk density of at least about 0.5 gram per cubic centimeter and the character of an angle of repose of at most about sixty degrees and wherein at least about fifty per cent by volume of said particles as dry particle have a diameter greater than five micrometers.
MEll '~DI~
Other embodiments of the present inventions include m~thods for the production of the embodied compositions. One embodied method is a method for producing a particulate composition comprising from about 20 to about 95 weight percent of the embodied particulate compositions of components selected from dithiocarbamates and bisdithiocarbamoyl disulfides, said method comprising (1) creating a slurry comprising particles of said components selected from dithiocarbamates and bisdithiocarbamoyl disulfides, said particles having a median particle size of from about 2 to about 7 micrometers; and (2) spray-drying said slurry to produce said particulate composition with a moisture content of from about ~ to about 10 weight percent of the embodied particulate compositions;
said creating and spray-drying being effective to significantly enhance the flowability of said particulate composition.
One preferred embodiment is the method ~Nherein said dithiocarbamate is mancozeb. In such method in the slurry said particles preferably can have a median particle size of from about 3 to about 6 micrometers.
Another embodied method is a method for producing a particulate composition havin~ enhanced flowability and comprising from about 50 to about 9~ weight percent of the embodiecl particulate compositions of components selected from dithiocarbamates and bisdithiocarbarrloyl disulfides, said method comprising (1) producing a ~irst slurry comprising (a) particles of said components selected frorn dithiocarbamates (preferably manganese dithiocarbamate) and bisdithiocarbamoyl disulfides, preferably in a weight percent of at least about ten percent of the weight of the slurry, (b) one or more water soluble zinc salt(s), preferably zinc chloride and/or zinc sulphate, and (c) water;
(2) wet-milling said first slurry to produce a second slurry h&ving a median particle size of about 2 to about 7 micrometers; and (3) spray-drying said second slurry to produce said particulate composition with a moisture content of about 2 to about 10 weight percent of the embodied particulate composition.
In one preferred method the first slurry comprises (a) at least ten (1.0) weight percent of a wet cake of maneb;
(b) manganese ions and zinc ions in a respecti~,e mol~ ratio of about ten to one; and (c) at least about forty t40) weight percent of water.
Even more preferably, the first slurry has at least about fifty (50) weight percent of a wet cake of maneb and the second slurry has a median particle size of about 5 micrometers.
In further embodiments, the first slurry composition further comprises 20937~7 at least about 2 weight percent of one or more additive(s) solected from stabilizing agents, dispersing agents, anti-foam agents, wetting agents, binding agents, filler agents and extending agents.
The following experiments illustrate embodiments of the present invention but are not intended to limit the scope thereof.
Experiment 1 -~rod~ Q~of Dithioca~am~Q~L~j~
Formulation of nine dithiocarbamate slurries was performed by admixing components to create each slurry with about the following composition:
ComponentWeight percent Wet Cake (about 60% Mn EBDC~) 72.07 Dispersant~ 2.60 Antifoam agent 0.02 Hexamethylenetetramine Stabilizer 1.42 ZnSO4 7H20 4.85 Water 1 9.04 "Mn EBDC" - manganese ethylenebisdithiocarbamat~
~ The production for each slurry was the same except that the slurries for samples 1-D, 1-W, 2-W, 3-W and 4-W had WafexrM dispersant as the dispersant and the slurries for samples 1-R, 2-R, 3-R and 4-R had Reax 100M~ dispersant as the dispersant.
After creation, each slurries were then wet-milled to a median particle size of about five (5) micn~meters.
~perimçnt ? - Production of Sam~le 1-p ~om~Qn ~93737 The slurry for Sample l-D from experiment 1 was spray dried with an inlet temperature of about 320-33~oC and an outlet temperature of about 80C to produce an intermediate composition which was subjected to a second drying stage to produce Sample 1-D.
Experiment 3 - PrnductiQn_of Sa..mple 1-W ~-W. 3-W~4-W. 1-R, 2-R. 3-R and 4-R ComDositiQns The procedure from experiment 1 was usod to produce eight (8) slurry samples, e.g., 1-W, 2-W, 3-W, and 4-W for the first set and 1-R, 2-R, 3-R, and 4-R for the second set. The eight slurry samples were th~n treated to a single spray-drying without a second drying stage. The respective spray drying conditions were an inlet temperature of 320-330C and the following outlet temperatures:
Samples Outlet Temperature 1 -W, 1 -R 11 5C
2-W, 2-R 1 00C
3-W, 3-R 90C
4-W, 4-R 70C
~937~7 Takle !
Initial Proper~ies Sample H2O Particle Size~ m ) ETU~
No. (%)~ _ _ 50%~ 20%~ (%)~
1-D 0.9 6.0 12.5 0.12 1-W 3.3 5.9 17.8 0.13 1 - R 4.0 6.4 17.3 0.13 2-R 6.8 6.3 17.9 0.12 2-W 7.0 5.6 17.2 0.097 3-R 9.8 7.2 18.9 0.071 3-W 10.3 6.2 18.0 0.087 4-R 12.0 14.9 48.6 0.057 4-W 13.1 14.9 43.1 0.024 After 2 weeks at 54C
Sampie H20 Particle Size (~m ) ETU
No. (%! 50% 90% ~ (%) 1 - D 0.79 6.0 12.4 0.28 1-W 2.7 7.2 22.7 0.22 1 - R 2.7 5.5 16.2 0.24 2-W 6.8 6.4 19.8 0.20 2-R 6.8 7.9 23.6 0.16 3-R 9.1 9.7 26.9 0.15 3-W 9.4 8.0 23.3 0.17 4-R 10.1 41.6 77.5 0.10 4-W 10.3 27.1 61.9 0.11 2~93~37 After 4 weeks at 54C
Sample H20 Particle Size(llm ) ETU
No. (%) . 50% 90% (/Q~
1-D 0.80 6~5 13.3 0.20 1-W 2.8 11.5 31.6 0.14 1-R 3.2 8.5 27.3 0.14 2-W 7.3 9.~ 2~.6 0.~2 2-R 7.1 1~.9 35.6 0.082 3-R 10.1 13.1 37.5 0.089 3-W 10.2 16.1 39.1 0.06B
4-R 11.1 30.8 51.1 0.023 4-W 10.5 40.9 73.2 O.û11 ~For the entire Table I all H2O and ETU "%" are by weight and all Particle Size "%" are by volume.
After redispersion in H2O.
ETU is ethylenethiourea Experiment 4 - Dry Particle Size Analysis Particle size analysis was performed to compare the particle size distribution in a low moisture dithiocarbamate composition (Sample A, same as 1-D hereinabove) and a relatively higher moisture dithiocarbamate composition (Sample B, prepared substantially same but with higher water content). The samples had the following characteristics:
~37~
TablÇ ll ~ampl~ A E~
~0 <1% 3.7%
Median Particle Size 5.9 ~m 29.9 ~m Particle Size Distribution 10% < 0.8 ~m < 7.1 ,um 50% S 5.9 ~lm s 29.9 ~Lm 75% S 10.4 ~lm S 42.7 llm 90% s 14.9 ~lm s 55.0 ~m The distribution is charted in Figure 1, which illustrates a significantly different distribution of particle diameters. Dry particle size analysis of other samples were performed with the following rasults.
20~373~
T~ble ILI
$amp!e ~ MediaQ~
1-D ~1 5.9 The following comparison of bulk densities were determined:
Table IV
~am~le HzOt%! BuLk ~nsity (g 1-D 0.98 0.45 2-W 7.0 0.71
Claims (42)
1. A particulate composition comprising one or more components selected from dithiocarbamates and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly enhance flowability of said particulate composition.
2. A particulate composition comprising one or more components selected from dithiocarbamates and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly reduce the dustiness of the composition.
3. A particulate composition comprising one or more components .
selected from dithiocarbamates and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly increase the bulk density of the composition.
selected from dithiocarbamates and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly increase the bulk density of the composition.
4. A particulate composition comprising one or more components selected from dithiocarbamates and bisdithiocarbamoyl disulfides and an effective amount of moisture content to significantly reduce the ethylenethiourea content of the composition.
5. The composition of claim 1 wherein said moisture content significantly increases the bulk density of the composition.
6. The composition of claim 5 wherein said moisture content significantly reduces the ethylenethiourea content of the composition.
7. The composition of claim 1 wherein said one or more component is selected from ethylenebisdithiocarbamatc metal salts, dimethyldithiocarbamate metal salts, propylenedithiocarbamate metal salts, metiram and thiram.
8. The composition of claim 7 wherein said ethylenebisdithiocarbamate metal salts are mancozeb, maneb and zineb.
9. The composition of claim 8 wherein said ethylenebisdithiocarbamate metal salt is mancozeb.
10. The composition of claim 8 wherein said ethylenebisdithiocarbamate metal salt is maneb or zineb.
11. The composition of claim 7 wherein said dithiocarbamate is thiram or metiram.
12. The composition of claim 7 wherein said dimethyldithiocarbamate metal salt is ziram.
13. The composition of claim 7 wherein the total weight of the one or more components selected from dithiocarbamate and bisdithiocarbamoyl disulfide is from about 20 to about 95 weight percent of said particulate composition.
14. The composition of claim 1 wherein the moisture content is from about 2.5 to about 20 % by weight of the composition.
15. The composition of claim 14 wherein the moisture content is from about 2.5 to about 10 % by weight of the composition.
16. The composition of claim 1 wherein the moisture content is comprised of one or more component(s) selected from water, alcohol, ammonia, carbon disulfide and glycol.
17. The composition of claim 16 wherein the moisture content is predominantly water.
18. The composition of claim 17 wherein the moisture content is from about 2.5 to about 10 % by weight of the composition.
19. The composition of claim 17 wherein the moisture content is predominantly water of hydration.
20. The composition of claim 1 after production having an initial ethylenethiourea content of less than about 0.1 weight percent of the composition.
21. The composition of claim 20 wherein said dithiocarbamate comprises mancozeb and said initial ethylenethiourea content is from about 0.01 to about 0.05 weight percent of the composition.
22. The composition of claim 1 wherein the ethylenethiourea content of said particulate composition maintained at a temperature of about 54 °C for two weeks after production of said composition is less than about 0.3 weight percent of the composition.
23. The composition of claim 1 wherein the ethylenethiourea content of said particulate composition maintained at a temperature of about 54 °C for two weeks after production of said composition is from about 0.10 to about 0.25 weight percent of the composition.
24. The composition of claim 1 wherein the ethylenethiourea content of said particulate composition maintained at a temperature of about 54 °C for four weeks after production of said composition is less than about 0.3 weight percent of the composition.
25. The composition of claim 24 wherein the ethylenethiourea content of said particulate composition maintained at a temperature of about 54 °C for four weeks after production of said composition is less than about 0.15 weight percent of the composition.
26. The composition of claim 3 having a bulk density of at least about 0.5 gram per cubic centimeter.
27. The composition of claim 26 wherein the bulk density is from about 0.5 to about 1.0 gram per cubic centimeter.
28. The composition of claim 1 wherein the median dry particle size ranges from about 20 to about 400 micrometers.
29. The composition of claim 28 having significantly reduced dustiness.
30. The composition of claim 28 wherein the volume percent amount of dry particles less than about 15 micrometers is at most about 50 percent of the volume percent amount of dry particles present when said composition is dried to 1 percent moisture content.
31. The composition of claim 30 wherein the volume percent amount of dry particles less than 15 micrometers is at most about 25 percent of the volume percent amount of dry particles present when said composition is dried to 1 percent moisture content based on total weight of the composition.
32. The composition of claim 30 wherein the volume percent amount of dry particles greater than about 20 micrometers is at least about 50 percent of the volume percent amount of dry particles present when said composition is dried to 1 percent moisture content based on total weight of the composition.
33. A method for producing a particulate composition comprising a fungicidally effective amount of from about 20 to about 95 weight percent dithiocarbamate, said method comprising (1 ) creating a slurry comprising particles of said dithiocarbamate, said particles having a median particle size of from about 2 to about 7 micrometers; and (2) spray-drying said slurry to produce said particulate composition with a moisture content of from about 2 to about 10 weight percent;
said creating and spray-drying being effective to significantly enhance the flowability of said particulate composition.
said creating and spray-drying being effective to significantly enhance the flowability of said particulate composition.
34. The method of claim 33 wherein said dithiocarbamate is mancozeb.
35. The method of claim 34 wherein in the slurry said particles have a median particle size of from about 3 to about 6 micrometers.
36. A method for producing a particulate composition having enhanced flowability and comprising a fungicidally effective amount of from about 50 to about 95 weight percent of a dithiocarbamate, said method comprising (1) producing a first slurry comprising (a) particles of manganese dithiocarbamate, (b) one or more water soluble zinc salt(s), and (c) water;
(2) wet-milling said first slurry to produce a second slurry having a median particle size of about 2 to about 7 micrometers; and (3) spray-drying said second slurry to produce said particulate composition with a moisture content of about 2 to about 10 weight percent.
(2) wet-milling said first slurry to produce a second slurry having a median particle size of about 2 to about 7 micrometers; and (3) spray-drying said second slurry to produce said particulate composition with a moisture content of about 2 to about 10 weight percent.
37. The method of claim 36 wherein said first slurry comprises (a) at least ten (10) weight percent of a wet cake of maneb;
(b) manganese ions and zinc ions in a respective mole ratio of about ten to one; and (c) at least about forty (40) weight percent of water.
(b) manganese ions and zinc ions in a respective mole ratio of about ten to one; and (c) at least about forty (40) weight percent of water.
38. The method of claim 37 wherein said first slurry has at least about fifty (50) weight percent of a wet cake of maneb and said second slurry has a median particle size of about 5 micrometer.
39. The method of claim 36 wherein the dithiocarbamate is present in said first slurry in a weight percent of at least about ten percent of the slurry.
40. The method of claim 36 wherein said first slurry composition further comprises at least about 2 weight percent of one or more additive(s) selected from stabilizing agents, dispersing agents, anti-foam agents, wetting agents, binding agents, filler agents and extending agents.
41. The method of claim 36 wherein said one or more water soluble zinc salt(s) comprises zinc chloride and/or zinc sulphate.
42. A composition comprising (a) particles comprising one or more components selected from ethylenebisdithiocarbamate metal salts, dimethyldithiocarbamate metal salts, propylenedithiocarbamate metal salts. metiram and thiram, and (b) water;
wherein the total weight of said components is from about 20 to about 90 weight per cent of said composition and wherein said composition has a bulk density of at least about 0.5 gram per cubic centimeter and the character of an angle of repose of at most about sixty degrees and wherein at least about fifty per cent by volume of said particles as dry particle have a diameter greater than five micrometers.
wherein the total weight of said components is from about 20 to about 90 weight per cent of said composition and wherein said composition has a bulk density of at least about 0.5 gram per cubic centimeter and the character of an angle of repose of at most about sixty degrees and wherein at least about fifty per cent by volume of said particles as dry particle have a diameter greater than five micrometers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87701092A | 1992-05-01 | 1992-05-01 | |
| US07/877,010 | 1992-05-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2093737A1 true CA2093737A1 (en) | 1993-11-02 |
Family
ID=25369071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002093737A Abandoned CA2093737A1 (en) | 1992-05-01 | 1993-04-08 | Fungicidal compositions and methods for production thereof |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPH06157212A (en) |
| KR (1) | KR940005225A (en) |
| AT (1) | ATE181483T1 (en) |
| CA (1) | CA2093737A1 (en) |
| DE (1) | DE69325412T2 (en) |
| ES (1) | ES2132186T3 (en) |
| LT (1) | LTIP505A (en) |
| PL (1) | PL298770A1 (en) |
| ZA (1) | ZA932905B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9426985B2 (en) | 2012-12-31 | 2016-08-30 | Dow Agrosciences Llc | Compositions and methods to modulate the rate of EBIS production from dithiocarbamate fungicides |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ293077B6 (en) * | 1996-08-02 | 2004-02-18 | American Cyanamid Company | Stable arylpyrrole particles, process of their preparation and compositions formed by a suspension concentrate containing such particles |
| CA2665598A1 (en) * | 2006-10-04 | 2008-04-17 | Dow Agrosciences Llc | Bisdithiocarbamate fungicide stabilization |
| BR112015022373B1 (en) * | 2013-03-13 | 2020-08-18 | Basf Se | WETTING COMPOSITION AND TREATED SOIL |
-
1993
- 1993-04-08 CA CA002093737A patent/CA2093737A1/en not_active Abandoned
- 1993-04-26 ZA ZA932905A patent/ZA932905B/en unknown
- 1993-04-29 AT AT93303381T patent/ATE181483T1/en active
- 1993-04-29 ES ES93303381T patent/ES2132186T3/en not_active Expired - Lifetime
- 1993-04-29 KR KR1019930007257A patent/KR940005225A/en not_active Application Discontinuation
- 1993-04-29 DE DE69325412T patent/DE69325412T2/en not_active Expired - Fee Related
- 1993-04-30 PL PL93298770A patent/PL298770A1/en unknown
- 1993-04-30 LT LTIP505A patent/LTIP505A/en not_active Application Discontinuation
- 1993-09-06 JP JP5221253A patent/JPH06157212A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9426985B2 (en) | 2012-12-31 | 2016-08-30 | Dow Agrosciences Llc | Compositions and methods to modulate the rate of EBIS production from dithiocarbamate fungicides |
Also Published As
| Publication number | Publication date |
|---|---|
| LTIP505A (en) | 1994-07-15 |
| KR940005225A (en) | 1994-03-21 |
| DE69325412T2 (en) | 2000-02-17 |
| ES2132186T3 (en) | 1999-08-16 |
| JPH06157212A (en) | 1994-06-03 |
| ATE181483T1 (en) | 1999-07-15 |
| PL298770A1 (en) | 1994-03-07 |
| ZA932905B (en) | 1994-01-07 |
| DE69325412D1 (en) | 1999-07-29 |
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