U.S. patent application number 14/978436 was filed with the patent office on 2016-05-19 for fumigant compositions and methods.
The applicant listed for this patent is HONEYWELL INTERNATIONAL INC.. Invention is credited to Cheryl L. Cantlon, David Nalewajek, Andrew J. Poss, Rajiv R. Singh.
Application Number | 20160135450 14/978436 |
Document ID | / |
Family ID | 48173006 |
Filed Date | 2016-05-19 |
United States Patent
Application |
20160135450 |
Kind Code |
A1 |
Poss; Andrew J. ; et
al. |
May 19, 2016 |
FUMIGANT COMPOSITIONS AND METHODS
Abstract
Fumigant compositions including hexafluoropropene or
1,1,3,3,3-pentafluoropropene, and methods of preparing such
compositions, are provided herein. The fumigant compositions may be
suitable for use as soil fumigant compositions and structural
fumigant compositions against a variety of undesirable species such
as weeds, nematodes, pathogens, animals and insects. The fumigant
compositions also have low toxicity and low Global Warming
Potential.
Inventors: |
Poss; Andrew J.; (Kenmore,
NY) ; Singh; Rajiv R.; (Getzville, NY) ;
Nalewajek; David; (West Seneca, NY) ; Cantlon; Cheryl
L.; (Clarence Center, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HONEYWELL INTERNATIONAL INC. |
MORRIS PLAINS |
NJ |
US |
|
|
Family ID: |
48173006 |
Appl. No.: |
14/978436 |
Filed: |
December 22, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13651565 |
Oct 15, 2012 |
9232788 |
|
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14978436 |
|
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61554623 |
Nov 2, 2011 |
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Current U.S.
Class: |
504/118 ;
514/746 |
Current CPC
Class: |
A01N 25/30 20130101;
A01N 43/20 20130101; A01N 29/02 20130101; A01N 41/12 20130101; A01N
35/02 20130101; A01N 33/18 20130101; A01N 43/08 20130101; A01N
47/08 20130101; A01N 29/02 20130101; A01N 29/02 20130101; A01N
35/02 20130101; A01N 41/12 20130101; A01N 43/08 20130101; A01N
43/20 20130101; A01N 47/08 20130101; A01N 47/14 20130101; A01N
2300/00 20130101 |
International
Class: |
A01N 29/02 20060101
A01N029/02 |
Claims
1. A method of eradicating undesirable species from a treatment
zone, the method comprising: contacting the treatment zone with a
fumigant composition comprising
hexafluoropropene,1,1,3,3,3-pentafluoropropene or a combination
thereof.
2. The method of claim 1, wherein the undesirable species include
one or more of weeds, nematodes or pathogens.
3. The method of claim 1, wherein the undesirable species include
insects or animals.
4. The method of claim 1, wherein the treatment zone comprises a
building or a vehicle.
5. The method of claim 1, wherein the treatment zone comprises
packaged goods.
6. The method of claim 1, wherein the treatment zone comprises a
field.
7. The method of claim 6, wherein the contacting step comprises
contacting soil with the fumigant composition.
8. The method of claim 7, wherein contacting soil comprises
contacting soil via drip irrigation.
9. The method of claim 7, wherein contacting soil comprises
contacting soil via shank injection.
10. The method of claim 1, wherein the fumigant composition is in
gaseous form.
11. The method of claim 1, wherein the fumigant composition is in
aqueous form.
12. The method of claim 1, wherein the fumigant composition further
comprises at least one of methyl iodide, chloropicrin, acrolein,
1,3-dichloropropene, dimethyl disulfide, furfural, propylene oxide
or metham sodium.
13. The method of claim 1, wherein the fumigant composition further
comprises at least one surfactant.
14. The method of claim 1. wherein the fumigant composition
comprises at least one odorant.
15. A fumigant composition comprising; hexafluoropropene,
1,1,3,3,3-pentafluoropropene or a combination thereof; at least one
component selected from methyl iodide, chloropicrin, acrolein,
1,3-dichloropropene, dimethyl disulfide, furfural, propylene oxide
metham sodium and combinations; and at least one surfactant.
16. The fumigant composition of claim 15, wherein the at least one
component comprises methyl iodide.
17. The fumigant composition of claim 15, consisting essentially of
hexafluoropropene or 1,1,3,3,3-pentafluoropropene, methyl iodide
and surfactant.
18. The fumigant composition of claim 15, wherein the surfactant
comprises a nonionic surfactant.
19. The fumigant composition of claim 15, wherein the surfactant
comprises a polysorbate.
20. A method of making a fumigant composition, the method
comprising combining methyl iodide, a surfactant and at least one
of hexafluoropropene and 1,1,3,3,3-pentafluoropropene in water.
Description
RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application Ser. No. 61/554,623 filed Nov. 2, 2011 entitled
"Fumigation Compositions and Methods," which application is
incorporated by reference herein.
FIELD OF THE INVENTION
[0002] The present technology relates to compositions and
formulations for soil and structural fumigation, methods of
preparing such formulations, and methods of fumigating soil and
structures with such compositions.
DESCRIPTION OF RELATED ART
[0003] Historically, methyl bromide (CH.sub.3Br) has been the most
widely used and most universal fumigant in the world. It is known
for being extremely effective as a herbicide, nematocide,
insecticide and fungicide. Consequently, it has been used
extensively for soil fumigation, as a commodity quarantine
treatment for exports and imports, to control a variety of pests on
numerous crops, and as a structural fumigant applied to building
surfaces. However, methyl bromide contributes to the depletion of
the ozone layer in the stratosphere. In accord with the Montreal
Protocol, the import and manufacture of methyl bromide in the
United States and other developed countries was banned in 2005.
[0004] Various compounds such as 1,3-dichloropropene, chloropicrin,
metham sodium, and methyl iodide have been identified as
alternatives to methyl bromide. These alternatives are commonly
applied as mixtures of two or more of the individual compounds in
order to attempt to produce a broader spectrum product similar to
methyl bromide.
[0005] As new fumigants are introduced, their global warming
potential (GWP) is also being scrutinized. GWP is a relative
measure of how much heat a greenhouse gas traps in the atmosphere.
It compares the amount of heat trapped by a certain mass of the gas
in question to the amount of heat trapped by a similar mass of
carbon dioxide. GWP is calculated over a specific time interval,
commonly 20, 100 or 500 years. GWP is expressed as a factor of
carbon dioxide (whose GMP is standardized to 1). For example, the
20 year GWP of methane is 56, which means if the same weights of
methane and carbon dioxide were introduced into the atmosphere,
that methane will trap 56 times more heat than the carbon dioxide
over the next 20 years.
SUMMARY OF THE INVENTION
[0006] Fumigant compositions and methods of preparing such
compositions are provided herein. The fumigant compositions may be
suitable for use as soil fumigant compositions and structural
fumigant compositions.
BRIEF DESCRIPTION OF THE FIGURES
[0007] FIG. 1 is a graphical representation of experimental
data.
[0008] FIG. 2 is a graphical representation of experimental
data.
DETAILED DESCRIPTION
[0009] Embodiments of the present invention include fumigant
compositions comprising an alkylene fluorocarbon including at least
one C.dbd.CF.sub.2 group. The fluorocarbon may also have a low
toxicity and a low GWP. For example, the fluorocarbon may have a
GWP of less than 1, more particularly, less than 0.5.
[0010] These fumigant compositions may be used against a variety of
different undesirable species, such as weeds, nematodes or
pathogens. In some embodiments, these fumigant compositions may be
used against a variety of different insects, including but not
limited to termites, cockroaches, mites and bed bugs. In some
embodiments, these fumigant compositions may be used against
animals such as gophers, mice, moles, rats and other rodent
pests.
[0011] These fumigant compositions may be used in a variety of
different treatment zones. Broadly, a treatment zone is a surface,
space or other volume that contains undesirable species. In some
embodiments, for example, the treatment zone may be a building such
as a warehouse or store or a vehicle such as a tractor trailer or a
rail car.
Fumigant Composition
[0012] The fumigant composition includes an alkylene fluorocarbon
including at least one C.dbd.CF.sub.2 group. In some embodiments,
the alkylene fluorocarbon has a three carbon backbone. In some
instances, smaller alkylene fluorocarbons have been found to
polymerize too quickly to be useful while larger alkylene
fluorocarbons have been found to be less effective.
[0013] In some embodiments, the fumigant composition comprises or
consists essentially of hexafluoropropene ("HFP"), or
1,1,3,3,3-pentafluoropropene ("1225zc"), which have the following
structures, respectively:
##STR00001##
[0014] Hexafluoropropene has a lifetime of only 5.8 days which
translates into a GWP of about 0.25. 1,1,3,3,3-Pentafluoropropene
also contains a highly reactive carbon-carbon double bond and
therefore has a GWP of less than 1. Both compounds also have
negligible ozone depletion potential.
[0015] The fluorocarbon may be present in an initial mixture (e.g.,
prior to diluting into a use solution) in an amount as low as about
1 weight percent (wt. %), in an amount as low as about 30 wt. %, in
an amount as low as about 40 wt. % or in an amount as low as about
50 wt. %. The fluorocarbon may be present in an initial mixture,
prior to dilution, in an amount as high as about 75 wt. %, in an
amount as high as about 85 wt. %, in an amount as high as about 95
wt. % or in an amount as high as about 99 wt. %. The fluorocarbon
may further be present within any range deliminated by any pair of
the foregoing values set forth in this paragraph. In some examples,
the fluorocarbon may have a boiling point of from about -50.degree.
C. to about 50.degree. C.
[0016] In addition to the fluorocarbon, the fumigant compositions
may also include at least one additional active ingredient.
Suitable actives for the fumigant compositions include, but are not
limited to, methyl iodide, chloropicrin, acrolein,
1,3-dichloropropene, dimethyl disulfide, furfural, metham sodium
and propylene oxide. In certain embodiments, both HFP and 1225zc
may be used with or without additional actives.
[0017] Methyl iodide can be present in the initial mixture in any
suitable amount, including for example, in an amount as low as
about 5 wt. %, in an amount as low as about 15 wt. % or in an
amount as low as about 25 wt. %. Methyl iodide can be present in
the initial mixture in an amount as high as about 50 wt. %, in an
amount as high as about 60 wt. % or in an amount as high as about
70 wt. %. Methyl iodide may further be present within any range
deliminated by any pair of the foregoing values set forth in this
paragraph.
[0018] The fumigant compositions according to embodiments of the
present invention may further include various additives. In one
embodiment, the fumigant composition may include at least one
surfactant. Suitable surfactants for use in fumigant compositions
can be ionic surfactants or non-ionic surfactants. Non-ionic
surfactants that can be suitable in fumigant compositions include,
but are not limited to: Arkopal.TM. (a nonylphenol ethoxylate),
Cetomacrogol.TM. 1000 (a polyethylene glycol), cetostearyl alcohol,
cetyl alcohol, cocamide DEA, cocamide MEA, decyl glucoside,
glyceryl laurate, lauryl glucoside, narrow range ethoxylates,
nonoxynols, NP-40, octaethylene glycol monododecyl ether, octyl
glucoside, oleyl alcohol, pentaethylene glycol, monododecyl ether,
poloxamer, polyglycerol polyricinoleate, polysorbate, polysorbate
20, polysorbate 40, polysorbate 60, polysorbate 80, sorbitan
monostearate, sorbitan tristearate, stearyl alcohol, Triton.TM.
X-100 (polyethylene oxide chain with an aromatic hydrocarbon
group), and Tween.TM. 80 (a polysorbate). In one specific example,
the surfactant can be a polysorbate, which can be polysorbate 20,
polysorbate 40, polysorbate 60 or polysorbate 80.
[0019] The surfactant can be included in an amount that is as low
as about 0.1 wt. %, in an amount as low as about 3 wt. % or in an
amount as low as about 5 wt. %. The surfactant can be included in
an amount that is as high as about 15 wt. %, in an amount as high
as about 30 wt. % or in an amount as high as about 50 wt. %. The
surfactant may further be present within any range deliminated by
any pair of the foregoing values set forth in this paragraph.
[0020] In some embodiments, the HFP or 1225zc can be diluted with a
suitable carrier solvent that can include at least one C3-C4
hydrofluorocarbon olefin or at least one hydrochlorofluorocarbon
olefin which preferably have a combination of desirable
environmental and functional properties. For example,
environmentally, the carrier solvents can have an ozone depletion
potential (ODP) that is zero or about zero. Carrier solvents may
also have a low global warming potential, which can preferably be
less than or equal to about 10 relative to CO2. Functionally,
carrier solvents are preferably volatile, non-toxic, and
non-flammable. Co-solvents for use with this technology include
mixtures of tetrafluoropropenes, hexafluorobutenes and
chlorotrifluoropropenes. The carrier solvents can include an
azeotropic or azeotrope-like mixture of the at least one C3-C4
hydrofluorocarbon olefin or the at least one
hydrochlorofluorocarbon olefin with an organic compound.
[0021] The solvent can be included in an amount that is as low as
about 1 wt. %. The solvent can be included in an amount as high as
about 5 wt. %, in an amount as high as about 50 wt. % or in an
amount as high as about 99 wt. %. The solvent may further be
present within any range deliminated by any pair of the foregoing
values set forth in this paragraph.
[0022] For safety purposes, the fumigant composition may include an
odorant such as banana oil or chloropicrin since certain
fluorocarbons including HFP and 1225zc have no detectable odor.
Application Techniques
[0023] The fumigant composition may be applied to soil or
structures as part of an aqueous solution or dispersion. The
fumigant composition may by applied by a number of different
procedures that are currently employed for soil and structural
treatments.
[0024] In some embodiments, soil fumigant may utilize either shank
injection or drip irrigation. In shank injection fumigant, the
chemical fumigant is applied to the soil by injection through
hollow shanks that are pulled through the soil, either at shallow
depths followed by plastic mulch film application, or at deep
depths followed by soil compaction.
[0025] Application of the chemical fumigant via drip irrigation
involves introducing and dispersing the chemical fumigant through
an existing irrigation system. This provides an advantage of
minimizing potential exposure to workers, as this can be done
without workers in the field.
[0026] The irrigation system may include one or more dripperlines
having a plurality of emitters therein. The emitters, also known as
drippers, can be of any suitable type, including for example
pre-punched holes or porous pipe. The emitters can be formed as an
integral part of a dripperline, or can be separately produced and
installed on or in the one or more dripperlines. The emitters can
be spaced apart at any suitable distance, including for example,
from about 8 inches apart to about 24 inches apart (from 200 mm to
600 mm apart).
[0027] In some examples, the one or more dripperlines can be placed
below the soil that is to be fumigated. Application of the fumigant
composition to the soil can include providing pressure to cause the
fumigant composition to flow through the one or more dripperlines
and exit the one or more dripperlines through the plurality of
emitters to contact and flow into the soil. Alternatively, the
fumigants may be applied to the soil by tractor mounted injectors,
manually in canisters or as a gas through lay-flat tubing.
[0028] The behavior of the fumigant compositions in use is a
function of their water solubility, volatility, hydrolysis and
degradation rates, and their sorption to soil organic matter and
clay. The physical and chemical properties of the fumigants, such
as: water solubility, vapor pressure, boiling point, Henry's
constant and half life in soil, are good indicators of how each
chemical will behave in the soil-air-water system. The efficacy of
a fumigant correlates to its distribution patterns in soils and
applications that maximize concentrations in the pest-infested zone
give better control.
[0029] For structural fumigation the chemicals may be heated to a
gas before introduction within a building, chamber, vehicle or
other space or structure. The space or structure is preferably
sealed with a tarpaulin, fumigant tape or gas impermeable sheeting.
In some embodiments, structural fumigant, particularly for rodents,
involves sealing the structure as tightly as possible. In some
embodiments, a 2 to 4 mil polyethylene cover may be used to wrap
the structure before providing the fumigant composition. In some
embodiments, the structure may subsequently be aerated to remove
the fumigant composition.
[0030] Stacked commodities may be treated by draping the
commodities with a gas-impermeable tarp or sheet that can be sealed
to an impermeable surface (such as a concrete floor) using, for
example, sand-filled tubes. After sufficient fumigant composition
has been released under the tarp, the space may be aerated to
remove remaining fumigant composition.
[0031] The fumigant compositions can be prepared by combining the
at least one fluorocarbon, the optional active, at least one
surfactant and water to form a fumigant composition. The fumigant
composition can be a solution or a homogeneous mixture, which can
be formed by mixing the combined initial mixture, the at least one
surfactant and the water under suitable conditions. In one example,
the fumigant compositions can be formed by mixing the components at
a temperature at or below about 60.degree. F. (15.5.degree.
C.).
EXAMPLE 1
[0032] Fumigant tests on seeds of the broadleaf species Abutilon
theophrasti Medik. and the grass weed species Lolium multiflorum
Lam. demonstrate that both HFP and 1125c completely prevented seed
germination. Since weeds are generally more resistant to fumigant
than most nematodes or soil-borne plant-pathogenic fungi (See Ohr
et al., "Methyl Iodide, an Ozone-Safe Alternative to Methyl Bromide
and a Soil Fumigant," Plant Disease, July 1996, pp. 731-735; See
also Zhang et al., "Effect of Soil Physical Factors on Methyl
Iodide and Methyl Bromide", Pestic. Sci. 1998, pp. 53, 71-79), this
result indicates that either of these chemicals can be employed as
a fumigant for the effective control of plant pathogens, nematodes,
bacteria and weeds.
[0033] In particular, in 440 mL pressure vessels, fourteen seeds of
Abutilon theophrasti Medik. and fifteen seeds of Lolium multiflorum
Lam. were thoroughly mixed with 50 mL (approximately 30 grams) of
soil and 6 mL of water. The filled vessels were kept at room
temperature for 20-24 hr to allow the seeds to imbibe water before
treatment. The vessels were sealed and evacuated, and then 80 ml,
160 ml and 440 ml respectively of gaseous 1225zc was added. The
vessels were thoroughly mixed and placed horizontally on the
laboratory bench at ambient temperature for two days. The contents
of each bottle were transferred to a plastic sterile Petri dish
containing 7 mL of water. The Petri dishes were sealed with
parafilm and incubated in the laboratory at ambient temperature.
After 10 days, the number of germinated seeds was counted. As shown
in Table 1 below, none of the seeds treated with 1225zc showed any
signs of germination.
TABLE-US-00001 TABLE 1 Seeds Germinated Abutilon theophrastic
Loliium multiflorum Fumigant Medik. Lam. Control 14 15 80 ml 1225zc
0 0 160 ml 1225zc 0 0 440 ml 1225zc 0 0
EXAMPLE 2
[0034] The same experiment was performed as described in Example 1
except that hexafluoropropene (HFP) was used as the active fumigant
composition. As shown in Table 2, no germination occurred under any
of the experimental concentrations.
TABLE-US-00002 TABLE 2 Seeds Germinated Abutilon theophrastic
Loliium multiflorum Fumigant Medik. Lam. Blank 14 15 80 ml HFP 0 0
160 ml HFP 0 0 440 ml HFP 0 0
[0035] The eradication of a broadleaf weed species (Abutilon
theophrastic Medik.) and a grass weed species (Loliium multiflorum
Lam.) indicates that HFP and 1225zc are suitable as general purpose
fumigant compositions to eradicate weeds, nematodes and soil-borne
plant-pathogenic fungi.
EXAMPLE THREE
[0036] Experimentation was carried out to determine the volatility
of aqueous fumigant compositions, both with and without inclusion
of a surfactant. In each case, the fluorocarbon was placed in a
chilled 500 ml Fischer Porter tube that was equipped with a vent to
remove any gases. The vessel was cooled to 0.degree. C. and was
charged with varying amounts of water, fluorocarbon and surfactant.
The temperature was equilibrated to 20.degree. C. and the reactor
was placed on a balance. The vent tube was opened and the weight
loss was recorded every 30 seconds.
[0037] In analyzing the effects of adding surfactant to an aqueous
solution of HFP, 10.11 grams of HFP was added to 39.71 grams of
water. In a separate experiment, 9.83 grams of HFP and 4.03 grams
of Tween.TM. 80 were added to 40.08 grams of water. FIG. 1 provides
a graphical representation of the numerical data comparing the
volatility of an aqueous solution of HFP, both with and without
inclusion of the Tween.TM. 80 nonionic surfactant. As can be seen,
inclusion of the surfactant provides for longer retention of the
HFP in solution.
[0038] In analyzing the effects of adding surfactant to an aqueous
solution of 1225zc, 10.78 grams of 1225zc were added to 39.69 grams
of water. In a separate experiment, 10.70 grams of 1225zc and 4.08
grams of Tween.TM. 80 were added to 40.15 grams of water. FIG. 2
provides a graphical representation of the numerical data comparing
the volatility of an aqueous solution of 1225zc, both with and
without inclusion of the Tween.TM. 80 nonionic surfactant. As can
be seen, inclusion of the surfactant provides for longer retention
of the 1225zc in solution.
* * * * *