U.S. patent application number 14/268896 was filed with the patent office on 2014-11-06 for enhanced nitrification inhibitor composition.
The applicant listed for this patent is DOW AGROSCIENCES LLC. Invention is credited to Raymond E. Boucher, JR., Mei Li, Martin C. Logan.
Application Number | 20140329678 14/268896 |
Document ID | / |
Family ID | 41054265 |
Filed Date | 2014-11-06 |
United States Patent
Application |
20140329678 |
Kind Code |
A1 |
Boucher, JR.; Raymond E. ;
et al. |
November 6, 2014 |
ENHANCED NITRIFICATION INHIBITOR COMPOSITION
Abstract
The present invention relates to an improved nitrification
inhibitor composition and its use in agricultural applications.
Inventors: |
Boucher, JR.; Raymond E.;
(Lebanon, IN) ; Li; Mei; (Westfield, IN) ;
Logan; Martin C.; (Indianapolis, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DOW AGROSCIENCES LLC |
Indianapolis |
IN |
US |
|
|
Family ID: |
41054265 |
Appl. No.: |
14/268896 |
Filed: |
May 2, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12393661 |
Feb 26, 2009 |
8741805 |
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14268896 |
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12009432 |
Jan 18, 2008 |
8377849 |
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12393661 |
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60881680 |
Jan 22, 2007 |
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Current U.S.
Class: |
504/101 ;
71/30 |
Current CPC
Class: |
C05G 3/90 20200201; Y02P
60/218 20151101; C05G 5/38 20200201; Y02P 60/21 20151101 |
Class at
Publication: |
504/101 ;
71/30 |
International
Class: |
C05G 3/00 20060101
C05G003/00 |
Claims
1. A microcapsule suspension formulation comprising: (a) a
suspended phase of a plurality of microcapsules having a volume
median particle size of from about 1 to about 10 microns, wherein a
microcapsule comprises: (1) a microcapsule wall produced by an
interfacial polycondensation reaction between a polymeric
isocyanate and a polyamine to form a polyurea shell having a weight
percentage of about 0.2 to about 15 percent of a total weight of
the microcapsule suspension formulation, and (2) a compound
encapsulated within the polyurea shell wherein said compound is
2-chloro-6-(trichloromethyl)pyridine; and (b) an aqueous phase
including a compound selected from the group consisting of: ionic
stabilizers, dispersants, emulsifiers, antifoams, and biocides.
2. The microcapsule suspension formulation according to claim 1
wherein the microcapsules have a volume median particle size of
from about 1 to about 5 microns.
3. The microcapsule suspension formulation according to claim 1
wherein the ratio of the suspended phase a) to the aqueous phase b)
is from about 1:0.75 to about 1:20.
4. The microcapsule suspension formulation according to claim 1
wherein the ratio of the suspended phase a) to the aqueous phase b)
is from about 1:1 to about 1:7.
5. The microcapsule suspension formulation according to claim 1
wherein the ratio of the suspended phase a) to the aqueous phase b)
is from about 1:1 to about 1:4.
6. The microcapsule suspension formulation according to claim 1
wherein the polymeric isocyanate is polymethylene
polyphenylisocyanate.
7. The microcapsule suspension formulation according to claim 1
wherein the polyamine is selected from ethylenediamine and
diethylenetriamine.
8. A fertilizer composition comprising: a nitrogen fertilizer and
the microcapsule suspension formulation according to claim 1.
9. The fertilizer composition according to claim 8 wherein the
nitrogen fertilizer is urea ammonium nitrate.
10. A method of suppressing the nitrification of ammonium nitrogen
in growth medium comprising applying the microcapsule suspension
formulation of claim 1 to said growth medium.
11. The method according to claim 10, wherein the formulation is
incorporated into the growth medium.
12. The method according to claim 10, wherein the formulation is
applied to a growth medium surface.
13. The method according to claim 10, wherein the formulation is
applied in combination with a pesticide or sequentially with a
pesticide.
14. The method according to claim 10, wherein the formulation is
applied with a nitrogen fertilizer.
15. The method according to claim 14, wherein the nitrogen
fertilizer is urea ammonium nitrate.
Description
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a continuation application of U.S.
patent application Ser. No. 12/393,661, which is a
continuation-in-part application of U.S. patent application Ser.
No. 12/009,432, filed Jan. 18, 2008 and now issued as U.S. Pat. No.
8,377,849, which claims the benefit of U.S. Provisional Application
Ser. No. 60/881,680 filed on Jan. 22, 2007, which are all expressly
incorporated by reference herein.
[0002] The present invention relates to an improved nitrification
inhibitor composition and its use in agricultural applications.
BACKGROUND
[0003] (Trichloromethyl)pyridine compounds, such as nitrapyrin,
have been used as nitrification inhibitors in combination with
fertilizers as described in U.S. Pat. No. 3,135,594, which is
herein incorporated by reference. These compounds maintain applied
ammonium nitrogen in the ammonium form (stabilized nitrogen), which
enhances crop performance. It would be desirable to broadly apply
these compounds with nitrogenous fertilizer at sowing time, but due
to potential volatility losses, these application methods are
generally unsatisfactory. In addition nitrapyrin has been added to
anhydrous ammonia, which by default must be injected into the
soil.
[0004] Other nitrapyrin formulations have been applied to the
surface of the soil, but must either be incorporated mechanically,
or watered into the soil within 8 hours after application to
overcome volatility losses. Finally, rapid or dump release capsule
formulations of nitrapyrin encapsulated with lignin sulfonates have
also been disclosed in U.S. Pat. No. 4,746,513, which is
incorporated herein by reference. However, although the release of
nitrapyrin is delayed by the encapsulation, the capsules release
all of the nitrapyrin upon contact with moisture, exhibiting the
same stability and volatility disadvantages of the prior
application methods. Additionally, these formulations are difficult
and costly to produce and cannot be used with liquid urea ammonium
nitrate ("UAN") fertilizers.
[0005] Polycondensation encapsulation, as disclosed in U.S. Pat.
No. 5,925,464, has been used to encapsulate agriculturally active
ingredients, particularly to enhance handling safety and storage
stability of the active ingredient by using polyurethane rather
than polyurea encapsulants.
[0006] However, there remains a need to deliver nitrification
inhibitors such as (trichloromethyl)pyridines, having greater long
term stability in the field environment, while maintaining the
level of efficacy of unencapsulated inhibitors.
SUMMARY
[0007] The present invention is a microcapsule suspension
formulation comprising: [0008] (a) a suspended phase of a plurality
of microcapsules having a volume median particle size of from about
1 to about 10 microns, wherein a microcapsule comprises: [0009] (1)
a microcapsule wall produced by an interfacial polycondensation
reaction between a polymeric isocyanate and a polyamine to form a
polyurea shell having a weight percentage of about 0.2 to about 15
percent of a total weight of the microcapsule suspension
formulation; and [0010] (2) a (trichloromethyl)pyridine compound
encapsulated within the polyurea shell; and [0011] (b) an aqueous
phase including an ionic stabilizer.
[0012] The microcapsule suspension formulation of the present
invention is stable and allows for delayed incorporation of
nitrogen in crops, thus providing agronomic and environmental
benefits. Surprisingly it has been discovered that a composition of
microcapsulated (trichloromethyl)pyridine compounds, such as
nitrapyrin, has superior performance when compared to
unencapsulated compositions of nitrapyrin, even when incorporated
into the soil.
DETAILED DESCRIPTION
[0013] (Trichloromethyl)pyridine compounds useful in the
composition of the present invention include compounds having a
pyridine ring which is substituted with at least one
trichloromethyl group and mineral acid salts thereof. Suitable
compounds include those containing chlorine or methyl substituents
on the pyridine ring in addition to a trichloromethyl group, and
are inclusive of chlorination products of methylpyridines such as
lutidine, collidine and picoline. Suitable salts include
hydrochlorides, nitrates, sulfates and phosphates. The
(trichloromethyl) pyridine compounds useful in the practice of the
present invention are typically oily liquids or crystalline solids
dissolved in a solvent. Other suitable compounds are described in
U.S. Pat. No. 3,135,594. A preferred (trichloromethyl)pyridine is
2-chloro-6-(trichloromethyl)pyridine, also known as nitrapyrin, and
the active ingredient of the product N-SERVE.TM.. (Trademark of Dow
AgroSciences LLC).
[0014] Examples of typical solvents which can be used to dissolve
crystalline (trichloromethyl)pyridine compounds include aromatic
solvents, particularly alkyl substituted benzenes such as xylene or
propylbenzene fractions, and mixed naphthalene and alkyl
naphthalene fractions; mineral oils; kerosene; dialkyl amides of
fatty acids, particularly the dimethylamides of fatty acids such as
the dimethyl amide of caprylic acid; chlorinated aliphatic and
aromatic hydrocarbons such as 1,1,1-trichloroethane and
chlorobenzene; esters of glycol derivatives, such as the acetate of
the n-butyl, ethyl, or methyl ether of diethyleneglycol and the
acetate of the methyl ether of dipropylene glycol; ketones such as
isophorone and trimethylcyclohexanone (dihydroisophorone); and the
acetate products such as hexyl or heptyl acetate. The preferred
organic liquids are xylene, alkyl substituted benzenes, such as
propyl benzene fractions, and alkyl naphthalene fractions.
[0015] In general, the amount of solvent employed, if desired, is
typically from about 40, preferably from about 50 to about 70,
preferably to about 60 weight percent, based on the total weight of
a (trichloromethyl)pyridine/solvent solution. The amount of
(trichloromethyl)pyridine within a (trichloromethyl)
pyridine/solvent solution is typically from about 30, preferably
from about 40 to about 60, preferably to about 50 weight percent,
based on the weight of a (trichloromethyl)pyridine/solvent
solution.
[0016] The microcapsules useful in the present invention can be
prepared by the polycondensation reaction of a polymeric isocyanate
and a polyamine to form a polyurea shell. Methods of
microencapsulation are well known in the art and any such method
can be utilized in the present invention to provide the capsule
suspension formulation. In general, the capsule suspension
formulation can be prepared by first mixing a polymeric isocyanate
with a (trichloromethyl)pyridine/solvent solution. This mixture is
then combined with an aqueous phase which includes an emulsifier to
form a two phase system. The organic phase is emulsified into the
aqueous phase by shearing until the desired particle size is
achieved. An aqueous crosslinking polyamine solution is then added
dropwise while stirring to form the encapsulated particles of
(trichloromethyl)pyridine in an aqueous suspension.
[0017] The desired particle size and cell wall thickness will
depend upon the actual application. The microcapsules typically
have a volume median particle size of from about 1 to about 10
microns and a capsule wall thickness of from about 10 to about 125
nanometers. In one embodiment, wherein the formulation of the
present invention will be incorporated immediately into a growth
medium, the desired particle size may be from about 2 to about 10
microns, with a cell wall of from about 10 to about 25 nanometers.
In another embodiment, requiring soil surface stability, the
desired particle size may be from about 1-5 microns, with cell wall
thicknesses of from about 75 to about 125 nanometers.
[0018] Other conventional additives may also be incorporated into
the formulation such as emulsifiers, dispersants, thickeners,
biocides, pesticides, salts and film-forming polymers.
[0019] Dispersing and emulsifying agents include condensation
products of alkylene oxides with phenols and organic acids, alkyl
aryl sulfonates, polyoxyalkylene derivatives of sorbitan esters,
complex ether alcohols, mahogany soaps, lignin sulfonates,
polyvinyl alcohols, and the like. The surface-active agents are
generally employed in the amount of from about 1 to about 20
percent by weight of the microcapsule suspension formulation.
[0020] The ratio of the suspended phase to the aqueous phase within
the microcapsule suspension formulation of the present invention is
dependent upon the desired concentration of
(trichloromethyl)pyridine compound in the final formulation.
Typically the ratio will be from about 1:0.75 to about 1:20.
Generally the desired ratio is about 1:1 to about 1:7, and is
preferably from about 1:1 to about 1:4.
[0021] The presence of a (trichloromethyl)pyridine compound
suppresses the nitrification of ammonium nitrogen in the soil or
growth medium, thereby preventing the rapid loss of ammonium
nitrogen originating from nitrogen fertilizers, organic nitrogen
constituents, or organic fertilizers and the like.
[0022] Generally, the microcapsule suspension formulation of the
present invention is applied such that the
(trichloromethyl)pyridine compound is applied to the soil or a
growth medium at a rate of from about 0.5 to about 1.5 kg/hectare,
preferably at a rate of from about 0.58 to about 1.2 kg/hectare.
The preferred amount can be easily ascertained by the application
preference, considering factors such as soil pH, temperature, soil
type and mode of application.
[0023] The microcapsule suspension formulation of the present
invention can be applied in any manner which will benefit the crop
of interest. In one embodiment the microcapsule suspension
formulation is applied to growth medium in a band or row
application. In another embodiment, the formulation is applied to
or throughout the growth medium prior to seeding or transplanting
the desired crop plant. In yet another embodiment, the formulation
can be applied to the root zone of growing plants.
[0024] Additionally, the microcapsule suspension formulation can be
applied with the application of nitrogen fertilizers. The
formulation can be applied prior to, subsequent to, or
simultaneously with the application of fertilizers.
[0025] The microcapsule suspension formulation of the present
invention has the added benefit that it can be applied to the soil
surface, without additional water or mechanical incorporation into
the soil for days to weeks. Alternatively, if desired, the
formulation of the present invention can be incorporated into the
soil directly upon application.
[0026] The microcapsule suspension formulation of the present
invention typically has a concentration of
(trichloromethyl)pyridine compound in amounts of from about 5,
preferably from about 10 and more preferably from about 15 to about
40, typically to about 35, preferably to about 30 and more
preferably to about 25 percent by weight, based on the total weight
of the microcapsule suspension formulation. The microcapsule
suspension formulation is then mixed with a solvent or water to
obtain the desired rate for application.
[0027] Soil treatment compositions may be prepared by dispersing
the microcapsule suspension formulation in fertilizers such as
ammonium or organic nitrogen fertilizer. The resulting fertilizer
composition may be employed as such or may be modified, as by
dilution with additional nitrogen fertilizer or with inert solid
carrier to obtain a composition containing the desired amount of
active agent for treatment of soil.
[0028] The soil may be prepared in any convenient fashion with the
microcapsule suspension formulation of the present invention,
including mechanically mixed with the soil; applied to the surface
of the soil and thereafter dragged or diced into the soil to a
desired depth; or transported into the soil such as by injection,
spraying, dusting or irrigation. In irrigation applications, the
formulation may be introduced to irrigation water in an appropriate
amount in order to obtain a distribution of the
(trichloromethyl)pyridine compound to the desired depth of up to 6
inches (15.24 cm.).
[0029] Surprisingly, once incorporated into the soil, the
microcapsule suspension formulation of the present invention
outperforms other nitrapyrin formulations, especially
unencapsulated versions. It was thought that the encapsulated
composition would not release nitrapyrin sufficiently to be as
effective as the non-encapsulated versions, wherein the diffusion
from the capsule would be too slow to provide a biological effect,
but in fact the opposite effect is observed.
[0030] Due to the controlled release of nitrapyrin in the
microcapsule suspension formulation of the present invention,
several advantages can be attained. First, the amount of nitrapyrin
can be reduced since it is more efficiently released into the soil
over an extended period of time. Additionally, the microcapsule
suspension formulation of the present invention can be applied and
left on the surface to be naturally incorporated into the soil,
without the need for mechanical incorporation if desired.
[0031] Additionally, the microcapsule suspension formulation of the
present invention can be combined or used in conjunction with
pesticides, including arthropodicides, bactericides, fungicides,
herbicides, insecticides, miticides, nematicides, nitrification
inhibitors such as dicyandiamide, urease inhibitors such as
N-(n-butyl)thiophosphoric triamide, and the like or pesticidal
mixtures and synergistic mixtures thereof. In such applications,
the microcapsule suspension formulation of the present invention
can be tank mixed with the desired pesticide(s) or they can be
applied sequentially.
[0032] Exemplary herbicides include, but are not limited to
acetochlor, alachlor, aminopyralid, atrazine, benoxacor,
bromoxynil, carfentrazone, chlorsulfuron, clodinafop, clopyralid,
dicamba, diclofop-methyl, dimethenamid, fenoxaprop, flucarbazone,
flufenacet, flumetsulam, flumiclorac, fluoroxypyr,
glufosinate-ammonium, glyphosate, halosulfuron-methyl,
imazamethabenz, imazamox, imazapyr, imazaquin, imazethapyr,
isoxaflutole, quinclorac, MCPA, MCP amine, MCP ester, mefenoxam,
mesotrione, metolachlor, s-metolachlor, metribuzin, metsulfuron
methyl, nicosulfuron, paraquat, pendimethalin, picloram,
primisulfuron, propoxycarbazone, prosulfuron, pyraflufen ethyl,
rimsulfuron, simazine, sulfosulfuron, thifensulfuron, topramezone,
tralkoxydim, triallate, triasulfuron, tribenuron, triclopyr,
trifluralin, 2,4-D, 2,4-D amine, 2,4-D ester and the like
[0033] Exemplary insecticides include, but are not limited to
[0034] 1,2 dichloropropane, 1,3 dichloropropene, [0035] abamectin,
acephate, acequinocyl, acetamiprid, acethion, acetoprole,
acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb,
aldrin, allethrin, allosamidin, allyxycarb, alpha cypermethrin,
alpha ecdysone, amidithion, amidoflumet, aminocarb, amiton,
amitraz, anabasine, arsenous oxide, athidathion, azadirachtin,
azamethiphos, azinphos ethyl, azinphos methyl, azobenzene,
azocyclotin, azothoate, [0036] barium hexafluorosilicate, barthrin,
benclothiaz, bendiocarb, benfuracarb, benoxafos, bensultap,
benzoximate, benzyl benzoate, beta cyfluthrin, beta cypermethrin,
bifenazate, bifenthrin, binapacryl, bioallethrin, bioethanomethrin,
biopermethrin, bistrifluoron, borax, boric acid, bromfenvinfos,
bromo DDT, bromocyclen, bromophos, bromophos ethyl, bromopropylate,
bufencarb, buprofezin, butacarb, butathiofos, butocarboxim,
butonate, butoxycarboxim, [0037] cadusafos, calcium arsenate,
calcium polysulfide, camphechlor, carbanolate, carbaryl,
carbofuran, carbon disulfide, carbon tetrachloride,
carbophenothion, carbosulfan, cartap, chinomethionat,
chlorantraniliprole, chlorbenside, chlorbicyclen, chlordane,
chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr,
chlorfenethol, chlorfenson, chlorfensulphide, chlorfenvinphos,
chlorfluazuron, chlormephos, chlorobenzilate, chloroform,
chloromebuform, chloromethiuron, chloropicrin, chloropropylate,
chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos methyl,
chlorthiophos, chromafenozide, cinerin I, cinerin II, cismethrin,
cloethocarb, clofentezine, closantel, clothianidin, copper
acetoarsenite, copper arsenate, copper naphthenate, copper oleate,
coumaphos, coumithoate, crotamiton, crotoxyphos, cruentaren A
&B, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate,
cyclethrin, cycloprothrin, cyenopyrafen, cyflumetofen, cyfluthrin,
cyhalothrin, cyhexatin, cypermethrin, cyphenothrin, cyromazine,
cythioate, [0038] d-limonene, dazomet, DBCP, DCIP, DDT,
decarbofuran, deltamethrin, demephion, demephion O, demephion S,
demeton, demeton methyl, demeton O, demeton O methyl, demeton S,
demeton S methyl, demeton S methylsulphon, diafenthiuron, dialifos,
diamidafos, diazinon, dicapthon, dichlofenthion, dichlofluanid,
dichlorvos, dicofol, dicresyl, dicrotophos, dicyclanil, dieldrin,
dienochlor, diflovidazin, diflubenzuron, dilor, dimefluthrin,
dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos,
dimetilan, dinex, dinobuton, dinocap, dinocap 4, dinocap 6,
dinocton, dinopenton, dinoprop, dinosam, dinosulfon, dinotefuran,
dinoterbon, diofenolan, dioxabenzofos, dioxacarb, dioxathion,
diphenyl sulfone, disulfuram, disulfoton, dithicrofos, DNOC,
dofenapyn, doramectin, [0039] ecdysterone, emamectin, EMPC,
empenthrin, endosulfan, endothion, endrin, EPN, epofenonane,
eprinomectin, esfenvalerate, etaphos, ethiofencarb, ethion,
ethiprole, ethoate methyl, ethoprophos, ethyl DDD, ethyl formate,
ethylene dibromide, ethylene dichloride, ethylene oxide,
etofenprox, etoxazole, etrimfos, EXD, [0040] famphur, fenamiphos,
fenazaflor, fenazaquin, fenbutatin oxide, fenchlorphos,
fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb,
fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fenpyroximate,
fenson, fensulfothion, fenthion, fenthion ethyl, fentrifanil,
fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron,
flubendiamide, flubenzimine, flucofuron, flucycloxuron,
flucythrinate, fluenetil, flufenerim, flufenoxuron, flufenprox,
flumethrin, fluorbenside, fluvalinate, fonofos, formetanate,
formothion, formparanate, fosmethilan, fospirate, fosthiazate,
fosthietan, fosthietan, furathiocarb, furethrin, furfural, [0041]
gamma cyhalothrin, gamma HCH, [0042] halfenprox, halofenozide, HCH,
HEOD, heptachlor, heptenophos, heterophos, hexaflumuron,
hexythiazox, HHDN, hydramethylnon, hydrogen cyanide, hydroprene,
hyquincarb, [0043] imicyafos, imidacloprid, imiprothrin,
indoxacarb, iodomethane, IPSP, isamidofos, isazofos, isobenzan,
isocarbophos, isodrin, isofenphos, isoprocarb, isoprothiolane,
isothioate, isoxathion, ivermectin [0044] jasmolin I, jasmolin II,
jodfenphos, juvenile hormone I, juvenile hormone II, juvenile
hormone III, [0045] kelevan, kinoprene, [0046] lambda cyhalothrin,
lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron,
lythidathion, [0047] malathion, malonoben, mazidox, mecarbam,
mecarphon, menazon, mephosfolan, mercurous chloride, mesulfen,
mesulfenfos, metaflumizone, metam, methacrifos, methamidophos,
methidathion, methiocarb, methocrotophos, methomyl, methoprene,
methoxychlor, methoxyfenozide, methyl bromide, methyl
isothiocyanate, methylchloroform, methylene chloride, metofluthrin,
metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin,
milbemycin oxime, mipafox, mirex, MNAF, monocrotophos, morphothion,
moxidectin, [0048] naftalofos, naled, naphthalene, nicotine,
nifluridide, nikkomycins, nitenpyram, nithiazine, nitrilacarb,
novaluron, noviflumuron, [0049] omethoate, oxamyl, oxydemeton
methyl, oxydeprofos, oxydisulfoton, [0050] paradichlorobenzene,
parathion, parathion methyl, penfluoron, pentachlorophenol,
permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone,
phosfolan, phosmet, phosnichlor, phosphamidon, phosphine,
phosphocarb, phoxim, phoxim methyl, pirimetaphos, pirimicarb,
pirimiphos ethyl, pirimiphos methyl, potassium arsenite, potassium
thiocyanate, pp' DDT, prallethrin, precocene I, precocene II,
precocene III, primidophos, proclonol, profenofos, profluthrin,
promacyl, promecarb, propaphos, propargite, propetamphos, propoxur,
prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos,
pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II,
pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon,
pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, [0051] quassia,
quinalphos, quinalphos, quinalphos methyl, quinothion, quantifies,
[0052] rafoxanide, resmethrin, rotenone, ryania, [0053] sabadilla,
schradan, selamectin, silafluofen, sodium arsenite, sodium
fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide,
spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,
sulcofuron, sulfuram, sulfluramid, sulfotep, sulfur, sulfuryl
fluoride, sulprofos, [0054] tau fluvalinate, tazimcarb, TDE,
tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,
tefluthrin, temephos, TEPP, terallethrin, terbufos,
tetrachloroethane, tetrachlorvinphos, tetradifon, tetramethrin,
tetranactin, tetrasul, theta cypermethrin, thiacloprid,
thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb,
thiofanox, thiometon, thionazin, thioquinox, thiosultap,
thuringiensin, tolfenpyrad, tralomethrin, transfluthrin,
transpermethrin, triarathene, triazamate, triazophos, trichlorfon,
trichlormetaphos 3, trichloronat, trifenofos, triflumuron,
trimethacarb, triprene, [0055] vamidothion, vamidothion,
vaniliprole, vaniliprole, [0056] XMC, xylylcarb, [0057] zeta
cypermethrin and zolaprofos.
[0058] Additionally, any combination of the above pesticides can be
used.
Additionally, Rynaxypyr.TM., a new crop protection chemistry from
DuPont with efficacy in controlling target pests can be used.
[0059] The following examples are provided to illustrate the
present invention. The examples are not intended to limit the scope
of the present invention and they should not be so interpreted.
Amounts are in weight parts or weight percentages unless otherwise
indicated.
EXAMPLES
Capsule Suspension Preparation
[0060] The weight percentages of the components for capsule
suspension preparation are summarized in Table I. Total batch size
is based on the weight of nitrapyrin used which is typically
approximately 25 g. The emulsifiers and crosslinking amines are
added as aqueous solutions of the indicated concentrations.
Microcapsule suspension formulation techniques are known in the
art. Additionally, it is also well know in the art that the order
of addition and corresponding procedures for producing microcapsule
suspension formulations may produce formulations having varying
physical characteristics such as viscosity. The following
preparation procedure is one illustrative embodiment of preparation
procedures, and should not be considered to limit the this
application.
[0061] Oil soluble monomer PAPI 27 (polymethylene
polyphenylisocyanate) (Dow Chemical), is added to a wide-mouthed
jar. Nitrapyrin (Dow AgroSciences) and Aromatic 200 (Exxon) are
then added in the form of a 50% nitrapyrin stock solution. The
resulting organic phase is combined with an aqueous solution of the
emulsifier(s) as indicated in Table I. The resulting two-phase
mixture is emulsified using a Silverson L4RT-A high-speed mixer
fitted with the 3/4 in. mixing tube and general purpose
emulsification head. Emulsification is achieved by first mixing at
relatively low speed (1000 rpm) with the end of the mixing tube
located in the aqueous phase to draw in the organic phase until
well emulsified. The speed is then increased in discrete
increments, measuring the particle size after each increase. This
process is continued until the desired particle size is obtained.
The water-soluble amine (diethylenetriamine (DETA, Aldrich) or
ethylenediamine (EDA, Aldrich) solution (10 wt. % in water) is then
added dropwise while stirring at a reduced rate. Following the
completion of the addition the resulting capsule suspension is
stirred for an additional minute. Following capsule formation,
Kelzan S (as 1.5% aqueous solution), Veegum (as 5% aqueous
solution), Proxel GXL and the balance of the water were added as
indicated in Table I and a final homogenization was performed with
the Silverson mixer.
TABLE-US-00001 TABLE I Example Compositions Weight Percent Material
Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Nitrapyrin 9.46 9.47 9.45
9.47 9.45 9.35 12.76 Aromatic 200 9.46 9.47 9.45 9.47 9.45 9.35
15.22 Dispersant/ 0.96.sup.1 0.48.sup.1 0.97.sup.1 0.48.sup.1
1.94.sup.1 2.43.sup.1 1.98.sup.4 Emulsifier (added as (added as
(added (added as (added as (added (added 5% aq, 2.5% aq, as 5% 2.5%
aq, 10% aq, as 10% as 5% sol'n) sol'n) aq, sol'n) sol'n) aq, aq,
sol'n) sol'n) sol'n) Thickener.sup.2 0.15 0.15 0.15 0.15 0.15 0.15
0.02 Emulsifier 0.99.sup.5 Suspending 0.2.sup.6 Aid PAPI-27 0.18
0.09 0.47 0.23 0.47 5.61 9.13 Amine 0.04.sup.7 0.02.sup.7
0.11.sup.7 0.06.sup.7 0.13.sup.8 1.35.sup.7 2.19.sup.7
Biocide.sup.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Total Water 79.65 80.22
79.30 80.04 78.31 71.68 57.40 Calculated 1.057 1.056 1.058 1.056
1.059 1.070 1.097 Density .sup.1Gohsenol GL-03 (polyvinyl alcohol
available from Nippon Gohsei) .sup.2Kelzan S-Xanthan gum (available
from CP Kelco) .sup.3Proxel GXL (1,2-Benzisothiazol-3(2H)-one
available from Arch Chemicals, Inc.) .sup.4Kraftsperse 25M
(available from MeadWestvaco) .sup.5Tergitol 15-S-7 (available from
The Dow Chemical Company) .sup.6Veegum (hectorite clay) (available
from R.T. Vanderbilt Co., Inc.) .sup.7EDA-ethylenediamine
(available from Aldrich) .sup.8DETA-diethylenetriamine (available
from Aldrich) Particle Size Measurement of Capsules
[0062] Capsule suspension particle size distributions are
determined using a Malvern Mastersizer 2000 light scattering
particle sizer fitted with a small volume sample unit. The volume
median distribution ("VMD") is reported for each formulation in
Table II.
TABLE-US-00002 TABLE II Particle Size and Cell Wall Thickness
Particle size Thickness Example (.mu.m) (nm) amine 1 5 10 EDA 2 10
10 EDA 3 5 25 EDA 4 10 25 EDA 5 2 10 DETA 6 2 100 EDA 7 2 100 EDA
Concentration of nitrapyrin is 100 g/L except for the formulation
of Example 7 which is 140 g/l in the formulation based on the
calculated density in Table I. EDA--ethylenediamine
DETA--diethylenetriamine
Calculation of Wall Thickness
[0063] The calculation of the amounts of capsule wall components
needed to achieve a target wall thickness is based on the geometric
formula relating the volume of a sphere to its radius. If a
core-shell morphology is assumed, with the core comprised of the
non wall-forming, water insoluble components (nitrapyrin, solvent)
and the shell made up of the polymerizable materials (oil- and
water-soluble monomers), then equation (1) holds, relating the
ratio of the volume of the core (V.sub.c) and the volume of the
core plus the volume of the shell (V.sub.s) to their respective
radii, where r.sub.s is radius of the capsule including the shell
and l.sub.s is thickness of the shell.
V c + V s V c = ( r s r s - l s ) 3 ( 1 ) ##EQU00001##
[0064] Solving equation (1) for the volume of the shell yields:
V S = V C ( ( r S r S - l S ) 3 - 1 ) ( 2 ) ##EQU00002##
[0065] Substituting masses (m.sub.i) and densities (d.sub.i) for
their respective volumes
[0066] (m.sub.s/d.sub.s=V.sub.s and m.sub.c/d.sub.c=V.sub.c, where
the subscript s or c refers to the shell or core, respectively) and
solving for the mass of the shell gives:
m S = m C S C ( ( r S r S - l S ) 3 - 1 ) ( 3 ) ##EQU00003##
[0067] It can be seen by comparing equations (2) and (3) that the
effect of the density ratio d.sub.s/d.sub.c is to apply a constant
correction factor when masses are used to calculate the amounts of
wall components needed to produce a capsule of desired size and
wall thickness. To be rigorous in the calculation of m.sub.s,
therefore, the densities of the core and shell must be known or at
least estimated from the weighted averages of the densities of each
of the components. However, the primary purpose of these
calculations is to use capsule wall thickness as a convenient
conceptual tool which would hopefully be helpful in understanding
capsule performance behavior and, therefore, in designing new
capsule formulations. Approximate values are felt to be sufficient
for this purpose. With this in mind the simplification is made of
setting the value of d.sub.s/d.sub.c to 1, which yields equation
(4).
m S .apprxeq. m C ( ( r S r S - l S ) 3 - 1 ) ( 4 )
##EQU00004##
[0068] Making the substitutions m.sub.c=m.sub.o-m.sub.OSM,
m.sub.s=m.sub.o+(f.sub.WSM/OSM))m.sub.OSM-m.sub.c, and
f.sub.WSM/OSM=m.sub.WSM/m.sub.OSM (the ratio of water soluble
monomer to oil soluble monomer), where m.sub.o is the total mass of
the oil components (nitrapyrin, solvent, oil-soluble monomer),
m.sub.OSM is the mass of the oil-soluble monomer, and m.sub.WSM is
the mass of the water-soluble monomer, and solving for m.sub.OSM
yields:
m OSM = m O ( ( r S r S - l S ) 3 - 1 ) f WSM / OSM + ( r S r S - l
S ) 3 ( 5 ) ##EQU00005##
[0069] For the determination of m.sub.OSM, the entire quantity of
m.sub.WSM is used in the calculation. In the present study the
water-soluble monomer is used at a 1:1 equivalent weight relative
to the oil-soluble monomer for all of the capsule suspension
preparations.
[0070] Conversely, the capsule wall thickness is calculated for
each of the capsule suspension preparations using the VMD particle
size for the value of r.sub.s and equation (6). These values are
included in Table II.
l S = r S ( ( m O + f WSM / OSM m OSM m O - m OSM ) 1 3 - 1 ) ( m O
+ f WSM / OSM m OSM m O - m OSM ) 1 3 ( 6 ) ##EQU00006##
Examples 1-5
[0071] A bulk sample of Drummer silty clay loam (sicl) soil is
collected, air-dried and crushed to pass a 2-mm screen. Following
the soil preparation, approximately 25 grams of the processed soil
is placed into beakers and treated with 7.5 ml water containing 10
mg N (as (NH.sub.4).sub.2SO.sub.4) and 0.0, 0.25 or 0.50 ppm
nitrapyrin (based on the weight of soil sample) using each of the
Example formulations 1-5. The treated soil is then evenly
distributed over the soil surface and immediately covered with
another 25 grams of soil. Three replications at each rate are
provided as well as three 50 gram soil samples without fertilizer
or inhibitor addition and three replications of N-Serve 24 (Dow
AgroSciences) treated soil. Once liquid is absorbed into soil, the
materials are mixed to attain even distribution of the
fertilizer/Example formulation. After mixing, water is added to
bring soil to field capacity. Beakers are unsealed, but covered to
reduce evaporation and maintained at room temperature,
approximately 25.degree. C. The amount of water lost from each
beaker is measured at 5-day intervals and replaced if the loss
exceeds 2.5 ml.
[0072] On day 7, 14, 21, 28, 35, 42, 49, and 56 after initiation of
the incubation, the soil contained in each individual beaker is
dried, ground, and mixed. A subsample is analyzed for NH4-N, as
described by Mulvaney, R. L. 1996; "Nitrogen-Inorganic Forms", pg
1123-1184. In D. L. Sparks (ed.) Methods of soil analysis: Part
3/SSSA Book Ser.5.SSSA, Madison, Wis. If less than 30% of the N
remains as ammonium in all replications of any treatment, analysis
of that treatment is ceased. Averages of the replications are
provided in Table III and Table IV.
TABLE-US-00003 TABLE III 0.5 ppm Nitrapyrin PPM NH.sub.4 Example
Week 1 Week 2 Week 3 Week 4 Week 5 No inhibitor 82.7 74.3 54.8 38.5
24.3 Control 1 82.3 84.2 67.7 59.6 48.9 2 82.5 79.5 71.3 63.1 49.8
3 81.8 78.8 67.6 64.3 46.7 4 88.5 81.8 77.5 55.6 46.1 5 82.9 78.0
70.8 57.0 51.7 N-Serve 24 87.1 75.5 64.9 55.6 37.4
TABLE-US-00004 TABLE IV 0.25 ppm Nitrapyrin PPM NH.sub.4 Example
Week 1 Week 2 Week 3 Week 4 Week 5 No inhibitor 82.7 74.3 54.8 38.5
24.3 Control 1 83.2 79.6 68.0 57.3 43.9 2 82.6 78.4 64.7 53.6 42.4
3 81.4 73.8 61.1 50.7 37.9 4 78.5 72.6 60.3 48.5 37.3 5 83.5 78.1
61.0 48.0 35.1 0.5 N-Serve 24 87.1 75.5 64.9 55.6 37.4
[0073] The microencapsulated formulations are compared to the
nitrapyrin N-Serve 24 (available from Dow AgroSciences) formulation
at the same rate. At Week 5 all five encapsulated formulations are
outperforming N-Serve 24, demonstrating that at the same rate they
provide superior residual nitrogen-stabilizing performance.
Examples 6 and 7
[0074] All of the following examples further include an ionic
stabilizer included in the aqueous phase. In the illustrative
example, sodium dioctylsulphosuccinate (Geropon SDS, available from
Rhodia) was used. Any other suitable ionic stabilizer may be
used.
[0075] Four replications each of Example 6 and 7 formulations, and
N-Serve 24 (0.5 lb a.i./acre; 0.58 kg/hectare) in combination with
urea ammonium nitrate (160 lb/acre; 181.5 kg/hectare), as well as
four replications of urea ammonium nitrate (160 lb N/acre; 181.5
kg/hectare) with 0 nitrification inhibitor treatment are applied to
Drummer sicl samples clear of vegetation.
[0076] Following application of the example formulations, the
formulations are incorporated immediately with moisture. Once
incorporation occurs, treatments are open to native rainfall and
environmental effects.
[0077] Soil samples are collected from each treatment and analyzed
for NH4-N as described by Mulvaney, as referenced previously, at
21, 28, 35, 42, 49 and 56 days after incorporation. Samples are
collected from 0-3 inch (0-7.6 cm), depths for 8 weeks with
additional samples collected from a 3-6 inch (7.6 cm-15.2 cm) depth
in weeks 7 and 8 after the first treatment is incorporated. On the
day of application, samples are collected from the 0-3 inch (0-7.6
cm) depth for NH.sub.4--N analysis.
[0078] The effectiveness of a nitrification inhibitor to keep
nitrogen in the ammonia form is measured by analyzing soil samples
for the presence of the ammonium molecule (NH.sub.4). Averages of
the replications are reported in Table V.
TABLE-US-00005 TABLE V Immediate incorporation of Controls and
Examples 6 and 7 PPM NH.sub.4 Week Week Week Example 3 Week 4 Week
5 6 Week 7 Week 8 9 N-Serve-24 27.4 15.6 10.2 12.6 8.3 4.2 7.0
Comparison UAN 16.7 13.3 5.3 7.0 7.2 4.0 5.0 Control Example 6 24.9
19.2 8.5 10.2 6.6 3.6 5.5 Example 7 26.4 22.0 16.3 12.4 9.1 5.8 6.0
UAN--Urea ammonium nitrate
[0079] In a further analysis, the nitrification inhibition of
Examples 6 and 7 are coupled with the surface stability of those
formulations. The UAN alone and the UAN+N-Serve treatments are
moisture incorporated on the day of application to the soil while
the two example formulations lay on the soil surface for a week
prior to incorporation. Plots awaiting moisture incorporation are
protected from moisture when rain events are threatening. Results
are listed in TABLE VI.
TABLE-US-00006 TABLE VI Delayed incorporation for Examples 6 and 7
PPM NH.sub.4 week week week week week week week week Examples 2 3 4
5 6 7 8 9 N-Serve-24 42.3 35.1 24.6 18.8 30.0 17.2 19.4 24.4
Comparison UAN Control 48.4 34.9 22.8 16.2 26.7 15.4 21.5 19.0
Example 6 50.6 41.6 30.2 22.4 34.0 18.6 27.0 28.5 Example 7 54.0
55.6 39.1 40.9 40.0 25.6 31.4 34.4
[0080] Both Examples 6 and 7 are more effective at nitrification
inhibition than N-Serve 24.
Examples 8 and 9
[0081] The weight percentages of the components for capsule
suspension preparation are listed in Table VII. Total batch size is
2.1 kg (Example 8) or 185 g (Example 9). Oil soluble monomer PAPI
27 (polymethylene polyphenylisocyanate, Dow Chemical), is added to
a wide-mouthed jar. N-Serve TG (Dow AgroSciences; 90 wt %
nitrapyrin) and Aromatic 200 (Exxon) are then added in the form of
a nitrapyrin technical concentrated stock solution. The resulting
homogeneous organic phase is combined with an aqueous solution
composed of Kraftsperse 25M, Tergitol 15-S-7, Geropon SDS, and
Proxcel GXL.
[0082] The resulting two-phase mixture is emulsified using a
Silverson L4RT-A highspeed mixer fitted with the % in. mixing tube
and general purpose emulsification head. Emulsification is achieved
by first mixing at relatively low speed (-1000 rpm) with the end of
the mixing tube located in the aqueous phase to draw in the organic
phase until well emulsified. The speed is then increased in
discrete increments, measuring the particle size after each
increase. This process is continued until the desired particle size
(2.5 micron) is obtained.
[0083] The water-soluble amine ethylenediamine aqueous solution (20
wt % in example 8; 30 wt % in example 9, example 10, and example
11) is then added dropwise while stirring at a reduced rate.
Following the completion of the addition the resulting capsule
suspension is stirred for an additional time to have the polyurea
shell forming reaction to be fully completed. Following capsule
formation, finishing phase including Avicel (as 5 wt % aqueous
solution, Kelzan (as 1.5 wt % aqueous solution), Proxel GXL and the
balance of the water were added as indicated in Table VII and a
final homogenization was performed with the Silverson mixer. The
dispersed phase, including nitrapyrin, aromatic 200, PAPI 27, and
ethylenediamine, is 49.55 wt % (example 8) or 55.94 wt % (example
9).
Example 10
[0084] The weight percentages of the components for capsule
suspension preparation are listed in Table VII. Total batch size is
100 kilograms. The processing is demonstrated in Scheme 1 (A). A
homogenous solution of N-Serve TG (Dow AgroSciences, 90 wt %
nitrapyrin) and Aromatic 200 (Exxon) is prepared by melting N-Serve
TG and adding it to the solvent. To this, the oil soluble monomer
PAPI 27 is added and mixed together to create the Oil Phase. The
Aqueous Phase is prepared by mixing Kraftsperse 25M,
Tergitol15-S-7, Geropon SDS, Proxel GXL, Antifoam 100 IND and water
into a homogeneous solution.
[0085] The Oil Phase and Aqueous Phase are metered together in a
1.25:1.0 ratio through a rotor/stator homogenizer cell to create an
emulsion of the desired particle size (2.5 micron). This process
continues until the oil phase is depleted. The batch is cooled down
to below 15.degree. C. before the amine is added. The 30 weight %
amine is added into the batch under agitation. The reaction vessel
is stirred for a minimum of 2 hours before the viscosity components
are added. The viscosity phase consists of 5 w/w % A vicel, 1.5 w/w
% Kelzan S, 1% Proxel GXL and water. Additional water is added if
necessary to achieve the target assay, then the batch is packaged
for final use.
Example 11
[0086] The weight percentages of the components for capsule
suspension preparation are listed in Table VII. Total batch size is
400 kilograms. The processing is demonstrated in Scheme 1 (B). A
homogenous solution of N-Serve TG (Dow AgroSciences, 90 wt %
nitrapyrin) and Aromatic 200 (Exxon) is prepared by melting N-Serve
TG and adding it to the solvent. To this, the oil soluble monomer
PAPI 27 is added and mixed together to create the Oil Phase. The
Aqueous Phase is prepared by mixing Kraftsperse 25M,
Tergitol15-S-7, Geropon SDS, Proxel GXL, Antifoam 100 IND and water
into a homogeneous solution.
[0087] The Oil Phase and Aqueous Phase are metered together in a
1.25:1.0 ratio through a rotor/stator homogenizer cell to create an
emulsion of the desired particle size (2.5 micron). This process
continues until the oil phase is depleted. The batch is cooled down
to below 15.degree. C. before the amine is added. The 30 weight %
amine is added into the batch by using a side stream circulation
stream pumping the emulsion at a rate of 100 liters per minute. The
amine is added in less than 10 minutes, preferably less than 5
minutes, to set the capsules walls. The reaction vessel is stirred
for a minimum of 2 hours before the viscosity components are added.
The viscosity phase consists of 5 w/w % A vicel, 1.5 w/w % Kelzan
S, 1% Proxel GXL and water. Additional water is added if necessary
to achieve the target assay, then the batch is packaged for final
use.
TABLE-US-00007 TABLE VII Example Compositions Weight Percent (wt %)
Material Example 8 Example 9 Example 10 Example 11 N-Serve TG 19.78
23.68 19.63 19.63 Aromatic 200 18.91 22.65 18.78 18.78 PAPI-27 8.87
7.72 8.80 8.80 Dispersant.sup.1 1.19 1.18 1.18 1.18
Emulsifier.sup.2 1.19 1.18 1.18 1.18 Ionic Stabilizer.sup.3 0.24
0.24 0.24 0.24 Antiformer.sup.4 0.09 0.09 0.09 Biocide.sup.5 0.12
0.12 0.12 0.12 Amine.sup.6 1.99.sup.a 1.90.sup.b 1.97.sup.c
2.17.sup.c Suspending Aid.sup.7 0.19 0.22 0.19 0.19 Thickener.sup.8
0.03 0.03 Total Water 47.52 41.02 47.79 47.59 .sup.1Kraftsperse 25M
(available from MeadWestvaco) .sup.2Tergitol 15-S-7 (available from
The Dow Chemical Company) .sup.3Geropon SDS (sodium
dioctylsulphosuccinate available from Rhodia) .sup.4Antiform 100
IND (available from Harcros Chemicals Inc.) .sup.5Proxel GXL
(1,2-Benzisothiazol-3(2H)-one available from Arch Chemicals, Inc.)
.sup.6EDA--ethylenediamine (available from Aldrich) in .sup.a20 wt
%; .sup.b50 wt %; and .sup.c30 wt % aqueous solution .sup.7Avecel
(available from FMC Biopolymer) .sup.8Kelzan S-Xanthan gum
(available from CP Kelco)
* * * * *