U.S. patent application number 13/531884 was filed with the patent office on 2012-10-18 for oil formulations.
Invention is credited to Edward Charles Kostansek.
Application Number | 20120264606 13/531884 |
Document ID | / |
Family ID | 39816810 |
Filed Date | 2012-10-18 |
United States Patent
Application |
20120264606 |
Kind Code |
A1 |
Kostansek; Edward Charles |
October 18, 2012 |
OIL FORMULATIONS
Abstract
There is provided a composition comprising an oil medium,
wherein particles are suspended in said oil medium, wherein said
particles comprise cyclopropene and molecular encapsulating agent,
and wherein said particles have median size, as measured by the
largest dimension, of 50 micrometer or less. Also provided are a
method of making such a composition and a method of treating plants
by contact with such a composition.
Inventors: |
Kostansek; Edward Charles;
(Buckingham, PA) |
Family ID: |
39816810 |
Appl. No.: |
13/531884 |
Filed: |
June 25, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12220407 |
Jul 24, 2008 |
8247459 |
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13531884 |
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60963297 |
Aug 3, 2007 |
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Current U.S.
Class: |
504/357 |
Current CPC
Class: |
A01N 27/00 20130101;
A01N 27/00 20130101; A01N 3/00 20130101; A01N 27/00 20130101; A01N
25/02 20130101; A01N 25/04 20130101; A01N 2300/00 20130101; A01N
25/30 20130101 |
Class at
Publication: |
504/357 |
International
Class: |
A01N 25/04 20060101
A01N025/04; A01P 21/00 20060101 A01P021/00; A01N 27/00 20060101
A01N027/00 |
Claims
1. A composition comprising an oil medium, wherein particles are
suspended in said oil medium, wherein said particles comprise
cyclopropene and molecular encapsulating agent, and wherein said
particles have median size, as measured by the largest dimension,
of 50 micrometer or less.
2. The composition of claim 1, wherein said oil medium comprises
one or more dispersant.
3. The composition of claim 1, wherein said oil medium comprises
one or more nonionic surfactant.
4. The composition of claim 1, wherein said oil medium comprises
one or more nonionic surfactant with HLB value of 3 to 4 and one or
more nonionic surfactant with HLB value of 8 to 10.
5. The composition of claim 1, wherein said oil medium is in the
form of droplets suspended in water.
6. The composition of claim 1, wherein said oil medium forms the
continuous medium of said composition.
7. The composition of claim 1, wherein said particle have median
aspect ratio of 20 or less.
8. A process for treating plants or plant parts comprising
contacting the composition of claim 1 with said plants or plant
parts.
9. A process for forming a composition, said process comprising
making a mixture comprising cyclopropene complex, oil, and
dispersant to a media mill; and milling said mixture to form
particles that comprise said cyclopropene complex, wherein said
particles have median size, as measured by the longest length, of
50 micrometer or less.
Description
[0001] This application claims the benefit of priority under 35
U.S.C. .sctn.119(e) of U.S. Provisional Patent Application No.
60/963,297 filed on Aug. 3, 2007.
BACKGROUND
[0002] For the use of cyclopropenes, the cyclopropene is often in
the form of a complex with a molecular encapsulating agent. Such a
complex is useful, for example, for use in treating plants or plant
parts by contacting the plants or plant parts with the complex in
order to bring about contact between the plants or plant parts and
the cyclopropene. Such treatment of plants or plant parts is often
effective at desirably interrupting one or more ethylene-mediated
process in the plants or plant parts. For example, such treatment
of plant parts can sometimes desirably delay unwanted ripening. For
another example, such treatment of crop plants prior to harvest can
sometimes improve the yield of the crop.
[0003] U.S. Pat. No. 6,313,068 discloses grinding and milling of
dried powder of a complex of cyclodextrin and
methylcyclopropene.
[0004] It is often useful to dissolve or suspend particles of such
a complex in a liquid. However, if water is the liquid, it is
sometimes found that contact between the water and the particles of
the complex causes release of cyclopropene from the complex earlier
than desired, and some or all of the cyclopropene is thus lost to
the surroundings or destroyed by a chemical reaction or a
combination thereof. Therefore, it is often desirable to suspend
such particles in oil. However, in the past, attempts to suspend
such particles in oil have found that such particles could not be
suspended effectively in oil, often because the suspensions could
not be sprayed properly, or because the suspensions had too high
viscosity at reasonable concentration of particles, or because the
suspensions were not stable, or because the suspensions had some
combination of these problems. The object of the present invention
is to provide suspensions in oil of particles containing
cyclopropene complex that solve one or more of these problems.
STATEMENT OF THE INVENTION
[0005] In one aspect of the present invention, there is provided a
composition comprising an oil medium, wherein particles are
suspended in said oil medium, wherein said particles comprise
cyclopropene and molecular encapsulating agent, and wherein said
particles have median size, as measured by the largest dimension,
of 50 micrometer or less.
DETAILED DESCRIPTION
[0006] The practice of the present invention involves the use of
one or more cyclopropene. As used herein, "a cyclopropene" is any
compound with the formula
##STR00001##
where each R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently
selected from the group consisting of H and a chemical group of the
formula:
-(L).sub.n-Z
where n is an integer from 0 to 12. Each L is a bivalent radical.
Suitable L groups include, for example, radicals containing one or
more atoms selected from H, B, C, N, O, P, S, Si, or mixtures
thereof. The atoms within an L group may be connected to each other
by single bonds, double bonds, triple bonds, or mixtures thereof.
Each L group may be linear, branched, cyclic, or a combination
thereof. In any one R group (i.e., any one of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4) the total number of heteroatoms (i.e., atoms
that are neither H nor C) is from 0 to 6. Independently, in any one
R group the total number of non-hydrogen atoms is 50 or less. Each
Z is a monovalent radical. Each Z is independently selected from
the group consisting of hydrogen, halo, cyano, nitro, nitroso,
azido, chlorate, bromate, iodate, isocyanato, isocyanido,
isothiocyanato, pentafluorothio, and a chemical group G, wherein G
is a 3 to 14 membered ring system.
[0007] The R.sup.1, R.sup.2, R.sup.3, and R.sup.4 groups are
independently selected from the suitable groups. The R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 groups may be the same as each other,
or any number of them may be different from the others. Among the
groups that are suitable for use as one or more of R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are, for example, aliphatic groups,
aliphatic-oxy groups, alkylphosphonato groups, cycloaliphatic
groups, cycloalkylsulfonyl groups, cycloalkylamino groups,
heterocyclic groups, aryl groups, heteroaryl groups, halogens,
silyl groups, other groups, and mixtures and combinations thereof.
Groups that are suitable for use as one or more of R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 may be substituted or unsubstituted.
Independently, groups that are suitable for use as one or more of
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 may be connected directly to
the cyclopropene ring or may be connected to the cyclopropene ring
through an intervening group such as, for example, a
heteroatom-containing group.
[0008] Among the suitable R.sup.1, R.sup.2, R.sup.3, and R.sup.4
groups are, for example, aliphatic groups. Some suitable aliphatic
groups include, for example, alkyl, alkenyl, and alkynyl groups.
Suitable aliphatic groups may be linear, branched, cyclic, or a
combination thereof. Independently, suitable aliphatic groups may
be substituted or unsubstituted.
[0009] As used herein, a chemical group of interest is said to be
"substituted" if one or more hydrogen atoms of the chemical group
of interest is replaced by a substituent. It is contemplated that
such substituted groups may be made by any method, including but
not limited to making the unsubstituted form of the chemical group
of interest and then performing a substitution. Suitable
substituents include, for example, alkyl, alkenyl, acetylamino,
alkoxy, alkoxyalkoxy, alkoxycarbonyl, alkoxyimio, carboxy, halo,
haloalkoxy, hydroxy, alkylsulfonyl, alkylthio, trialkylsilyl,
dialkylamino, and combinations thereof. An additional suitable
substituent, which, if present, may be present alone or in
combination with another suitable substituent, is
-(L).sub.m-Z
where m is 0 to 8, and where L and Z are defined herein above. If
more than one substituent is present on a single chemical group of
interest, each substituent may replace a different hydrogen atom,
or one substituent may be attached to another substituent, which in
turn is attached to the chemical group of interest, or a
combination thereof.
[0010] Among the suitable R.sup.1, R.sup.2, R.sup.3, and R.sup.4
groups are, for example, substituted and unsubstituted
aliphatic-oxy groups, such as, for example, alkenoxy, alkoxy,
alkynoxy, and alkoxycarbonyloxy.
[0011] Also among the suitable R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 groups are, for example, substituted and unsubstituted
alkylphosphonato, substituted and unsubstituted alkylphosphato,
substituted and unsubstituted alkylamino, substituted and
unsubstituted alkylsulfonyl, substituted and unsubstituted
alkylcarbonyl, and substituted and unsubstituted
alkylaminosulfonyl, including, for example, alkylphosphonato,
dialkylphosphato, dialkylthiophosphato, dialkylamino,
alkylcarbonyl, and dialkylaminosulfonyl.
[0012] Also among the suitable R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 groups are, for example, substituted and unsubstituted
cycloalkylsulfonyl groups and cycloalkylamino groups, such as, for
example, dicycloalkylaminosulfonyl and dicycloalkylamino.
[0013] Also among the suitable R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 groups are, for example, substituted and unsubstituted
heterocyclyl groups (i.e., aromatic or non-aromatic cyclic groups
with at least one heteroatom in the ring).
[0014] Also among the suitable R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 groups are, for example, substituted and unsubstituted
heterocyclyl groups that are connected to the cyclopropene compound
through an intervening oxy group, amino group, carbonyl group, or
sulfonyl group; examples of such R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 groups are heterocyclyloxy, heterocyclylcarbonyl,
diheterocyclylamino, and diheterocyclylaminosulfonyl.
[0015] Also among the suitable R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 groups are, for example, substituted and unsubstituted aryl
groups. Suitable substituents are those described herein above. In
some embodiments, one or more substituted aryl group is used in
which at least one substituent is one or more of alkenyl, alkyl,
alkynyl, acetylamino, alkoxyalkoxy, alkoxy, alkoxycarbonyl,
carbonyl, alkylcarbonyloxy, carboxy, arylamino, haloalkoxy, halo,
hydroxy, trialkylsilyl, dialkylamino, alkylsulfonyl, sulfonylalkyl,
alkylthio, thioalkyl, arylaminosulfonyl, and haloalkylthio.
[0016] Also among the suitable R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 groups are, for example, substituted and unsubstituted
heterocyclic groups that are connected to the cyclopropene compound
through an intervening oxy group, amino group, carbonyl group,
sulfonyl group, thioalkyl group, or aminosulfonyl group; examples
of such R.sup.1, R.sup.2, R.sup.3, and R.sup.4 groups are
diheteroarylamino, heteroarylthioalkyl, and
diheteroarylaminosulfonyl.
[0017] Also among the suitable R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 groups are, for example, hydrogen, fluoro, chloro, bromo,
iodo, cyano, nitro, nitroso, azido, chlorato, bromato, iodato,
isocyanato, isocyanido, isothiocyanato, pentafluorothio; acetoxy,
carboethoxy, cyanato, nitrato, nitrito, perchlorato, allenyl;
butylmercapto, diethylphosphonato, dimethylphenylsilyl,
isoquinolyl, mercapto, naphthyl, phenoxy, phenyl, piperidino,
pyridyl, quinolyl, triethylsilyl, trimethylsilyl; and substituted
analogs thereof.
[0018] As used herein, the chemical group G is a 3 to 14 membered
ring system. Ring systems suitable as chemical group G may be
substituted or unsubstituted; they may be aromatic (including, for
example, phenyl and napthyl) or aliphatic (including unsaturated
aliphatic, partially saturated aliphatic, or saturated aliphatic);
and they may be carbocyclic or heterocyclic. Among heterocyclic G
groups, some suitable heteroatoms are, for example, nitrogen,
sulfur, oxygen, and combinations thereof. Ring sysytems suitable as
chemical group G may be monocyclic, bicyclic, tricyclic,
polycyclic, Spiro, or fused; among suitable chemical group G ring
systems that are bicyclic, tricyclic, or fused, the various rings
in a single chemical group G may be all the same type or may be of
two or more types (for example, an aromatic ring may be fused with
an aliphatic ring).
[0019] In some embodiments, G is a ring system that contains a
saturated or unsaturated 3:membered ring, such as, for example, a
substituted or unsubstituted cyclopropane, cyclopropene, epoxide,
or aziridine ring.
[0020] In some embodiments, G is a ring system that contains a 4
membered heterocyclic ring; in some of such embodiments, the
heterocyclic ring contains exactly one heteroatom. Independently,
in some embodiments, G is a ring system that contains a
heterocyclic ring with 5 or more members; in some of such
embodiments, the heterocyclic ring contains 1 to 4 heteroatoms.
Independently, in some embodiments, the ring in G is unsubstituted;
in other embodiments, the ring system contains 1 to 5 substituents;
in some of the embodiments in which G contains substituents, each
substituent is independently chosen from the substituents described
herein above. Also suitable are embodiments in which G is a
carbocyclic ring system.
[0021] In some embodiments, each G is independently a substituted
or unsubstituted phenyl, pyridyl, cyclohexyl, cyclopentyl,
cycloheptyl, pyrolyl, furyl, thiophenyl, triazolyl, pyrazolyl,
1,3-dioxolanyl, or morpholinyl. Among these embodiments include
those embodiments, for example, in which G is unsubstituted or
substituted phenyl, cyclopentyl, cycloheptyl, or cyclohexyl. In
some of these embodiments, G is cyclopentyl, cycloheptyl,
cyclohexyl, phenyl, or substituted phenyl. Among embodiments in
which G is substituted phenyl are embodiments, for example, in
which there are 1, 2, or 3 substituents. Independently, also among
embodiments in which G is substituted phenyl are embodiments, for
example, in which the substituents are independently selected from
methyl, methoxy, and halo.
[0022] Also contemplated are embodiments in which R.sup.3 and
R.sup.4 are combined into a single group, which is attached to the
number 3 carbon atom of the cyclopropene ring by a double bond.
Some of such compounds are described in US Patent Publication
2005/0288189.
[0023] In some embodiments, one or more cyclopropenes are used in
which one or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is
hydrogen. In some embodiments, R.sup.1 or R.sup.2 or both R.sup.1
and R.sup.2 is hydrogen. Independently, in some embodiments,
R.sup.3 or R.sup.4 or both R.sup.3 and R.sup.4 is hydrogen. In some
embodiments, R.sup.2, R.sup.3, and R.sup.4 are hydrogen.
[0024] In some embodiments, one or more of R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 is a structure that has no double bond.
Independently, in some embodiments, one or more of R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 is a structure that has no triple
bond. Independently, in some embodiments, one or more of R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 is a structure that has no halogen
atom substituent.
[0025] Independently, in some embodiments, one or more of R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 is a structure that has no
substituent that is ionic.
[0026] In some embodiments, one or more of R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 is hydrogen or (C.sub.1-C.sub.10)alkyl. In
some embodiments, each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is
hydrogen or (C.sub.1-C.sub.8)alkyl. In some embodiments, each of
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is hydrogen or
(C.sub.1-C.sub.4)alkyl. In some embodiments, each of R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 is hydrogen or methyl. In some
embodiments, R.sup.1 is (C.sub.1-C.sub.4)alkyl and each of R.sup.2,
R.sup.3, and R.sup.4 is hydrogen. In some embodiments, R.sup.1 is
methyl and each of R.sup.2, R.sup.3, and R.sup.4 is hydrogen, and
the cyclopropene is known herein as "1-MCP."
[0027] In some embodiments, a cyclopropene is used that has boiling
point at one atmosphere pressure of 50.degree. C. or lower; or
25.degree. C. or lower; or 15.degree. C. or lower. Independently,
in some embodiments, a cyclopropene is used that has boiling point
at one atmosphere pressure of -100.degree. C. or higher;
-50.degree. C. or higher; or -25.degree. C. or higher; or 0.degree.
C. or higher.
[0028] The cyclopropenes applicable to this invention may be
prepared by any method. Some suitable methods of preparation of
cyclopropenes are the processes disclosed in U.S. Pat. Nos.
5,518,988 and 6,017,849.
[0029] The composition of the present invention includes at least
one molecular encapsulating agent. In some embodiments, at least
one molecular encapsulating agent encapsulates one or more
cyclopropene or a portion of one or more cyclopropene. A complex
that contains a cyclopropene molecule or a portion of a
cyclopropene molecule encapsulated in a molecule of a molecular
encapsulating agent is known herein as a "cyclopropene
complex."
[0030] In some embodiments, at least one cyclopropene complex is
present that is an inclusion complex. In such an inclusion complex,
the molecular encapsulating agent forms a cavity, and the
cyclopropene or a portion of the cyclopropene is located within
that cavity. In some of such inclusion complexes, there is no
covalent bonding between the cyclopropene and the molecular
encapsulating agent. Independently, in some of such inclusion
complexes, there is no ionic bonding between the cyclopropene and
the molecular encapsulating complex, whether or not there is any
electrostatic attraction between one or more polar moiety in the
cyclopropene and one or more polar moiety in the molecular
encapsulating agent.
[0031] Independently, in some of such inclusion complexes, the
interior of the cavity of the molecular encapsulating agent is
substantially apolar or hydrophobic or both, and the cyclopropene
(or the portion of the cyclopropene located within that cavity) is
also substantially apolar or hydrophobic or both. While the present
invention is not limited to any particular theory or mechanism, it
is contemplated that, in such apolar cyclopropene complexes, van
der Waals forces, or hydrophobic interactions, or both, cause the
cyclopropene molecule or portion thereof to remain within the
cavity of the molecular encapsulating agent.
[0032] The cyclopropene molecular encapsulation agent complexes can
be prepared by any means. In one method of preparation, for
example, such complexes are prepared by contacting the cyclopropene
with a solution or slurry of the molecular encapsulation agent and
then isolating the complex, using, for example, processes disclosed
in U.S. Pat. No. 6,017,849. For example, in one method of making a
complex in which cyclopropene is encapsulated in a molecular
encapsulating agent, the cyclopropene gas is bubbled through a
solution of molecular encapsulation agent in water, from which the
complex first precipitates and is then isolated by filtration. In
some embodiments, complexes are made by the above method and, after
isolation, are dried and stored in solid form, for example as a
powder, for later addition to useful compositions.
[0033] The amount of molecular encapsulating agent can usefully be
characterized by the ratio of moles of molecular encapsulating
agent to moles of cyclopropene. In some embodiments, the ratio of
moles of molecular encapsulating agent to moles of cyclopropene is
0.1 or larger; or 0.2 or larger; or 0.5 or larger; or 0.9 or
larger. Independently, in some of such embodiments, the ratio of
moles of molecular encapsulating agent to moles of cyclopropene is
2 or lower; or 1.5 or lower.
[0034] Suitable molecular encapsulating agents include, for
example, organic and inorganic molecular encapsulating agents.
Suitable organic molecular encapsulating agents include, for
example, substituted cyclodextrins, unsubstituted cyclodextrins,
and crown ethers. Suitable inorganic molecular encapsulating agents
include, for example, zeolites. Mixtures of suitable molecular
encapsulating agents are also suitable. In some embodiments, the
encapsulating agent is alpha-cyclodextrin, beta-cyclodextrin,
gamma-cyclodextrin, or a mixture thereof. In some embodiments of
the invention, alpha-cyclodextrin is used. The preferred
encapsulating agent will vary depending upon the structure of the
cyclopropene or cyclopropenes being used. Any cyclodextrin or
mixture of cyclodextrins, cyclodextrin polymers, modified
cyclodextrins, or mixtures thereof can also be utilized pursuant to
the present invention. Some cyclodextrins are available, for
example, from Wacker Biochem Inc., Adrian, Mich. or Cerestar USA,
Hammond, Ind., as well as other vendors.
[0035] In the practice of the present invention, one or more oils
are used. As used herein, an "oil" is a compound that is liquid at
25.degree. C. and 1 atmosphere pressure and that has a boiling
point at 1 atmosphere pressure of 30.degree. C. or higher. As used
herein, "oil" does not include water, does not include surfactants
(as described herein), and does not include dispersants (as
described herein).
[0036] In some embodiments, one or more oil may be used that has
boiling point of 50.degree. C. or higher; or 75.degree. C. or
higher; or 100.degree. C. or higher. In some embodiments, every oil
that is used has boiling point of 50.degree. C. or higher. In some
embodiments, every oil that is used has boiling point of 75.degree.
C. or higher. In some embodiments, every oil that is used has
boiling point of 100.degree. C. or higher. Independently, in some
of the embodiments that use oil, one or more oil may be used that
has an average molecular weight of 100 or higher; or 200 or higher;
or 500 or higher. In some embodiments, every oil that is used has
average molecular weight of 100 or higher. In some embodiments,
every oil that is used has average molecular weight of 200 or
higher. In some embodiments, every oil that is used has average
molecular weight of 500 or higher.
[0037] An oil may be either a hydrocarbon oil (i.e., an oil whose
molecule contains only atoms of carbon and hydrogen) or a
non-hydrocarbon oil (i.e., an oil whose molecule contains at least
at least one atom that is neither carbon nor hydrogen).
[0038] Some suitable hydrocarbon oils are, for example, straight,
branched, or cyclic alkane compounds with 6 or more carbon atoms.
Some other suitable hydrocarbon oils, for example, have one or more
carbon-carbon double bond, one or more carbon-carbon triple bond,
or one or more aromatic ring, possibly in combination with each
other and/or in combination with one or more alkane group. Some
suitable hydrocarbon oils are obtained from petroleum distillation
and contain a mixture of compounds, along with, in some cases,
impurities. Hydrocarbon oils obtained from petroleum distillation
may contain a relatively wide mixture of compositions or may
contain relatively pure compositions. In some embodiments,
hydrocarbon oils are used that contain 6 or more carbon atoms. In
some embodiments, hydrocarbon oils are used that contain 18 or
fewer carbon atoms. In some embodiments, every hydrocarbon oil that
is used contains 18 or fewer carbon atoms. In some embodiments,
every hydrocarbon oil that is used contains 6 or more carbon atoms.
Some suitable hydrocarbon oils include, for example, hexane,
decane, dodecane, hexadecane, diesel oil, refined paraffinic oil
(e.g., Ultrafine.TM. spray oil from Sun Company), and mixtures
thereof. In some embodiments, every oil that is used is a
hydrocarbon oil.
[0039] Among embodiments that use non-hydrocarbon oil, some
suitable non-hydrocarbon oils are, for example, fatty
non-hydrocarbon oils. "Fatty" means herein any compound that
contains one or more residues of fatty acids. Fatty acids are
long-chain carboxylic acids, with chain length of at least 4 carbon
atoms. Typical fatty acids have chain length of 4 to 18 carbon
atoms, though some have longer chains. Linear, branched, or cyclic
aliphatic groups may be attached to the long chain. Fatty acid
residues may be saturated or unsaturated, and they may contain
functional groups, including for example alkyl groups, epoxide
groups, halogens, sulfonate groups, or hydroxyl groups, that are
either naturally occurring or that have been added. Some suitable
fatty non-hydrocarbon oils are, for example, fatty acids; esters of
fatty acids; amides of fatty acids; dimers, trimers, oligomers, or
polymers thereof; and mixtures thereof.
[0040] Some of the suitable fatty non-hydrocarbon oils, are, for
example, esters of fatty acids. Such esters include, for example,
glycerides of fatty acids. Glycerides are esters of fatty acids
with glycerol, and they may be mono-, di-, or triglycerides. A
variety of triglycerides are found in nature. Most of the naturally
occurring triglycerides contain residues of fatty acids of several
different lengths and/or compositions. Some suitable triglycerides
are found in animal sources such as, for example, dairy products,
animal fats, or fish. Further examples of suitable triglycerides
are oils found in plants, such as, for example, coconut, palm,
cottonseed, olive, tall, peanut, safflower, sunflower, corn,
soybean, linseed, tung, castor, canola, citrus seed, cocoa, oat,
palm, palm kernel, rice bran, cuphea, or rapeseed oil.
[0041] Among the suitable triglycerides, independent of where they
are found, are those, for example, that contain at least one fatty
acid residue that has 14 or more carbon atoms. Some suitable
triglycerides have fatty acid residues that contain 50% or more by
weight, based on the weight of the residues, fatty acid residues
with 14 or more carbon atoms, or 16 or more carbon atoms, or 18 or
more carbon atoms. One example of a suitable triglyceride is
soybean oil.
[0042] Suitable fatty non-hydrocarbon oils may be synthetic or
natural or modifications of natural oils or a combination or
mixture thereof. Among suitable modifications of natural oils are,
for example, alkylation, hydrogenation, hydroxylation, alkyl
hydroxylation, alcoholysis, hydrolysis, epoxidation, halogenation,
sulfonation, oxidation, polymerization, and combinations thereof.
In some embodiments, alkylated (including, for example, methylated
and ethylated) oils are used. One suitable modified natural oil is
methylated soybean oil.
[0043] Also among the suitable fatty non-hydrocarbon oils are
self-emulsifying esters of fatty acids.
[0044] Another group of suitable non-hydrocarbon oils is the group
of silicone oils. Silicone oil is an oligomer or polymer that has a
backbone that is partially or fully made up of --Si--O-- links.
Silicone oils include, for example, polydimethylsiloxane oils.
Polydimethylsiloxane oils are oligomers or polymers that contain
units of the
##STR00002##
where at least one of the units has X1=CH.sub.3. In other units, X1
may be any other group capable of attaching to Si, including, for
example, hydrogen, hydroxyl, alkyl, alkoxy, hydroxyalkyl,
hydroxyalkoxy, alkylpolyalkoxyl, substituted versions thereof, or
combinations thereof. Substituents may include, for example,
hydroxyl, alkoxyl, polyethoxyl, ether linkages, ester linkages,
amide linkages, other substituents, or any combination thereof. In
some embodiments, every oil that is used is a silicone oil.
[0045] In some suitable polydimethylsiloxane oils, all X1 groups
are groups that are not hydrophilic. In some suitable
polydimethylsiloxane oils, all X1 groups are alkyl groups. In some
suitable polydimethylsiloxane oils, all X1 groups are methyl. In
some embodiments, every silicone oil is a polydimethylsiloxane oil
in which all X1 groups are methyl. In some suitable
polydimethylsiloxanes, at least one unit has an X1 group that is
not methyl; if more than one non-methyl X1 unit is present, the
non-methyl X1 units may be the same as each other, or two or more
different non-methyl X1 units may be present. Polydimethylsiloxane
oils may be end-capped with any of a wide variety of chemical
groups, including, for example, hydrogen, methyl, other alkyl, or
any combination thereof. Also contemplated are cyclic
polydimethylsiloxane oils.
[0046] Mixtures of suitable oils are also suitable.
[0047] The practice of the present invention involves particles
suspended in an oil medium. The oil medium may be any of the oils
described herein above. By "suspended" herein is meant that the
particles are insoluble or only slightly soluble in the oil and
that the particles are distributed throughout the oil, which forms
a continuous medium around the particles. The system of particles
suspended in oil is known herein as a "suspension." The suspensions
of the present invention are stable; that is, under normal
conditions of 25.degree. C., 1 atmosphere pressure, and normal
gravity, upon storage for 1 day, most of the particles (at least
80% by weight, based on the total dry weight of the particles) will
not settle to the bottom of the container. In some embodiments, the
amount of particles that settles to the bottom of the container on
storage, by weight based on the total dry weight of the particles,
is 10% or less, or 5% or less, or 2% or less, or 1% or less.
Independently, in some embodiments, suspensions are used that are
stable upon storage for 2 days, or 5 days, or 10 days.
[0048] The particles of the present invention that are suspended in
an oil medium have median size, as measured by the largest
dimension, of 50 micrometer or less. That is, the collection of
particles is assessed to determine the size. One suitable method of
assessment, for example, is inspection using a microscope. Images
of particles, for example, those images obtained in a microscope,
may be inspected and assessed by eye, possibly with reference to
length standards, or alternatively the images may be inspected and
assessed by appropriate image analysis methods, such as, for
example, computer programs.
[0049] In embodiments in which the particles are not spherical, it
is useful to characterize the particles by the largest dimension of
each particle. A collection of particles may be characterized by
the median value of the largest dimension. That is, half of the
particles in the collection, by weight, will have largest dimension
that is larger than the median value of the collection. In the
practice of the present invention, when the collection of particles
suspended in the oil medium is assessed, that median value is 50
micrometers or less. In some embodiments, particles are used in
which that median value is 20 micrometers or less; or 10
micrometers or less; or 5 micrometers or less; or 2 micrometers or
less.
[0050] An independent measure of a particle is the aspect ratio,
which is the ratio of the largest dimension of the particle to the
smallest dimension of the particle. The aspect ratio is independent
of the size of the particle. In some embodiments of the present
invention, the collection of particles suspended in oil medium has
aspect ratio of 20 or lower; or 10 or lower; or 5 or lower; or 2 or
lower.
[0051] The particles that are suspended in the oil medium are
solid. That is, the particles are partially or fully made of
material that is in the solid state. Each particle may or may not
be porous or may or may not have one or more void or may or may not
have one or more cavity, and each pore or void or cavity (if
present) may or may not be partially or fully occupied by material
that is solid, liquid, or gas. The system of particles suspended in
the oil medium is synonymously known as a "dispersion."
[0052] The particles that are suspended in the oil medium contain
cyclopropene and molecular encapsulating agent. In some
embodiments, some or all of the cyclopropene that is present in the
composition is part of a cyclopropene complex. While the present
invention is not limited to any particular theory or model, it is
contemplated that most or all of the cyclopropene molecules that
are present in the composition are present in the form of molecules
that are part of cyclopropene complexes. It is further contemplated
that any cyclopropene molecules in the composition that are not
part of a cyclopropene complex are present, for example, in
solution, adsorbed on an interface, some other location, or a
combination thereof. In some embodiments, the amount of
cyclopropene that is present as part of a cyclopropene complex, by
weight based on the total amount of cyclopropene in the
composition, is 80% or more; or 90% or more; or 95% or more; or 99%
or more.
[0053] In some embodiments of the present invention, the oil medium
comprises one or more dispersant. It is contemplated that some or
all of the dispersant is dissolved in the oil, that some or all of
the dispersant is located on the particle surface (i.e., at the
interface between the particle and the oil medium), or a
combination thereof. Additionally, it is contemplated that small
amounts of dispersant (or none) may be located in one or more other
places, such as, for example, at the surface of the oil, on the
walls of the container, in a complex with a molecular encapsulating
agent, or a combination thereof.
[0054] As defined herein, a "dispersant" is a compound that is
capable of assisting a solid particle to form a stable suspension
in a liquid medium. In some embodiments, suitable dispersants have
one or more hydrophilic group. Independently, in some embodiments,
suitable dispersants have multiple hydrophobic groups. Some
suitable hydrophobic groups include, for example, organic groups
with 8 or more consecutive carbon atoms. In some embodiments,
hydrophobic groups are present that have 10 or more consecutive
carbon atoms. Independent of the number of carbon atoms, such
organic groups may be linear, cyclic, branched or a combination
thereof. Independently, such organic groups may be hydrocarbons or
may be substituted. Independently, such organic groups may be
saturated or unsaturated.
[0055] Some suitable dispersants have 2 or more hydrophobic groups
per molecule, or 3 or more, or 4 or more, or 5 or more. In some
embodiments, every dispersant has 4 or more hydrophobic groups per
molecule. In some embodiments, every dispersant has 5 or more
hydrophobic groups per molecule.
[0056] Independent of the nature of the hydrophobic group, some
suitable dispersants have one or more hydrophilic group. Some
suitable hydrophilic groups include, for example, groups that are
capable of ionizing in water over certain ranges of pH, such as,
for example, carboxyl groups, sulfate groups, sulfonate groups, and
amine groups. Other suitable hydrophilic groups are nonionic. Some
suitable nonionic hydrophilic groups include, for example, segments
of polymers that, if they existed independently as polymers, would
be soluble in water. Such hydrophilic segments of polymers include,
for example, polyethylene glycol segments.
[0057] In embodiments in which dispersant is used, the molecule of
which contains both hydrophobic groups and at least one hydrophilic
group, the groups may be attached to the dispersant molecule in any
way. For example, some suitable dispersants are block copolymers
with at least one block that is a polyethylene glycol segment and
at least one block that contains plural hydrophobic groups. One
example of a block containing plural hydrophobic groups is segment
of poly(12-hydroxystearic acid). Another example of a block
containing plural hydrophobic groups is a segment of an alkyd
polymer. Alkyd polymers are copolymers of polyols, polybasic acids,
and fatty acids or triglyceride oils.
[0058] As used herein, a nonionic dispersant is a dispersant in
which all of the hydrophilic groups are nonionic. In some
embodiments, at least one nonionic dispersant is used. In some
embodiments, every dispersant that is used is nonionic.
[0059] One useful characteristic of a nonionic molecule is the HLB
value, which is defined by the equation
HLB=20*M.sub.H/M
where M.sub.H is the molecular mass of the hydrophilic portion of
the molecule, and M is the molecular mass of the molecule.
[0060] A molecule of interest, whether ionic or nonionic, may be
characterized by the acid number (synonymously called "acid
value"), which is the milligrams of KOH needed to neutralize the
molecule of interest, per gram of the molecule of interest. One
method of testing the acid number is shown in ASTM D-7253. It is
understood that some details of the test (such as, for example,
selection of solvent and/or indicator) may be adapted as necessary
for the specific molecule of interest.
[0061] In some embodiments in which one or more nonionic dispersant
is used, one or more of the dispersants has HLB of higher than 4,
or HLB of 5 or higher. Independently, in some embodiments, one or
more dispersant is used that has HLB of lower than 8, or HLB of 7
or lower. In some embodiments, every dispersant that is used has
HLB that is 5 to 7.
[0062] Independent of the HLB value of the dispersant, in some
embodiments in which one or more nonionic dispersant is used, one
or more of the dispersants has acid number, in units of mg KOH/g,
of 10 or lower; or 9 or lower; or 8 or lower. Independently, in
some embodiments in which one or more nonionic dispersant is used,
one or more of the dispersants has acid number, in units of mg
KOH/g, of 2 or higher; or 4 or higher; or 6 or higher. In some
embodiments, every dispersant that is used has acid number that is
6 to 8 mg KOH/g.
[0063] In some embodiments, one or more dispersant is used that has
acid number that is 6 to 8 mg KOH/g or higher, where the same
dispersant also has HLB that is 5 to 7.
[0064] In some embodiments, one or more surfactant is used.
"Surfactant," as used herein, is synonymous with "emulsifier" and
means a compound that assists the formation of a stable suspension
of oil droplets in water. The molecule of a surfactant compound
contains at least one hydrophilic group and at least one
hydrophobic group. Surfactants are normally classified according to
the nature of the hydrophilic group. Suitable surfactants include,
for example, anionic surfactants, cationic surfactants, nonionic
surfactants, amphoteric surfactants, and mixtures thereof.
[0065] In embodiments in which one or more anionic surfactant is
used, some suitable anionic surfactants include, for example, the
sulfosuccinates (including, for example, alkaline salts of mono-
and dialkyl sulfosuccinates), the sulfates, and the sulfonates,
including, for example, alkaline salts of alkyl sulfates. In some
embodiments, no anionic surfactant is used.
[0066] Among embodiments in which one or more cationic surfactant
is used, some suitable cationic surfactants include, for example,
amine surfactants and quaternary ammonium salt surfactants. In some
embodiments, no cationic surfactant is used.
[0067] In some embodiments, one or more nonionic surfactant is
used. Among embodiments in which one or more nonionic surfactant is
used, some suitable nonionic surfactants include, for example,
fatty ethoxylates, fatty acid esters of polyhydroxy compounds,
amide oxides, alkyl oxide block copolymers, silicone based nonionic
surfactants, fluorosurfactants, and mixtures thereof.
[0068] Suitable fatty ethoxylates include, for example, ethoxylates
of fatty alcohols, ethoxylates of fatty acids, ethoxylates of fatty
ethanolamides, and ethoxylates of fatty amines. Suitable
ethoxylates of fatty alcohols include, for example, ethoxylates of
fatty alcohols that have any combination of the following
characteristics: linear or branched; primary or secondary; alkyl or
alkyl aryl. In some embodiments, one or more fatty ethoxylate is
used that is an aryl alkyl ethoxylate, a fatty alcohol ethoxylate,
or a mixture thereof.
[0069] Suitable silicone based nonionic surfactants include, for
example, those with the formula
##STR00003##
where n is 1 to 5, m is 0 to 4, and Q is
##STR00004##
where p is 1 to 6, and q is 3 to 20. In some embodiments, n is 1.
Independently, in some embodiments, m is zero. Independently, in
some embodiments, p is 3. Independently, in some embodiments, q is
7 or 8 or a mixture thereof.
[0070] One further example of a suitable nonionic surfactant is
Atplus 595.
[0071] Mixtures of suitable surfactants are also suitable.
[0072] Nonionic surfactants may be usefully characterized by HLB,
as defined herein above. In some embodiments, one or more nonionic
surfactant is used that has HLB of 3 to 4. Independently, in some
embodiments, one or more nonionic surfactant is used that has HLB
of 8 to 10. In some embodiments, a mixture of surfactants is used
that includes one or more nonionic surfactant with HLB of 3 to 4
and also one or more nonionic surfactant with HLB of 8 to 10.
[0073] In some embodiments (herein called "continuous oil"
embodiments), the continuous medium of the composition of the
present invention is the oil medium in which the particles are
suspended. In some continuous oil embodiments, one or more
surfactant is present in the composition. In some continuous oil
embodiments, no surfactant is present in the composition.
Independently, in some continuous oil embodiments, little or no
water is present; that is, in such embodiments, if any water is
present, the amount of water, by weight based on the weight of the
composition, 5% or less; or 2% or less; or 1% or less; or 0.5% or
less; or 0.1% or less.
[0074] In some continuous oil embodiments, the amount of
cyclopropene is 1 gram of cyclopropene per liter of oil ("g/L") or
more; or 2 g/L or more, or 5 g/L or more, or 10 g/L or more, or 20
g/L or more. Independently, in some continuous oil embodiments, the
amount of cyclopropene is 200 g/L or less; or 100 g/L or less; or
50 g/L or less
[0075] In some continuous oil embodiments, the amount of
dispersant, by weight based on the weight of the composition, is
0.1% or more; or 0.2% or more; or 0.5% or more, or 0.75% or more.
Independently, in some continuous oil embodiments, the amount of
dispersant, by weight based on the weight of the composition, is
20% or less; or 10% or less; or 5% or less; or 2% or less.
[0076] In some continuous oil embodiments, the amount of
surfactant, by weight based on the weight of the composition, is
0.5% or more; or 1% or more, or 2% or more. Independently in some
continuous oil embodiments, the amount of surfactant, by weight
based on the weight of the composition, is 20% or less; or 10% or
less. In some continuous oil embodiments, no surfactant is
present.
[0077] In some embodiments (herein called "continuous water"
embodiments), the continuous medium of the composition of the
present invention is an aqueous medium. An aqueous medium is a
liquid the contains 50% or more water, by weight based on the
weight of the aqueous medium. In some embodiments, an aqueous
medium is used that has an amount of water, by weight based on the
weight of the aqueous medium, of 75% or more, or 90% or more, or
95% or more. In continuous water embodiments, the oil medium in
which the particles are suspended is divided into discrete
droplets, and these droplets are suspended in the aqueous
medium.
[0078] In some continuous water embodiments, one or more surfactant
is present in the composition. In some continuous water
embodiments, one or more nonionic surfactant is present in the
composition. In some continuous water embodiments, one or more
nonionic surfactant with HLB of 3 to 4 is present in the
composition, and one or more surfactant with HLB of 8 to 10 is also
present in the composition. In some embodiments, the choice of one
or more surfactant is made because that surfactant is well suited
to emulsify the droplets of the specific oil that is used as the
oil medium in that embodiment.
[0079] In some continuous water embodiments, the amount of
cyclopropene, by weight based on the weight of the composition, is
10 parts per million (ppm) or greater; or 20 ppm or greater; or 50
ppm or greater. Independently, in some continuous water
embodiments, the amount of cyclopropene, by weight based on the
weight of the composition, is 500 ppm or lower; or 200 ppm or
lower.
[0080] In some continuous water embodiments, the amount of
dispersant, by weight based on the weight of the composition, is
2.5 ppm or greater; or 10 ppm or greater; or 50 ppm or greater; or
200 ppm or greater. Independently, in some continuous water
embodiments, the amount of dispersant, by weight based on the
weight of the composition, is 1250 ppm or lower; or 1000 ppm or
lower, or 750 ppm or lower.
[0081] In some continuous water embodiments, the amount of
surfactant, by weight based on the weight of the composition, is,
by weight of dry surfactant based on the weight of the composition,
0.02% or more, or 0.05% or more, or 0.1% or more, or 0.2% or more.
Independently, in some continuous water embodiments, the amount of
surfactant, by weight based on the weight of the composition, is,
by weight of dry surfactant based on the weight of the composition,
2% or less, or 1% or less, or 0.5% or less.
[0082] The composition of the present invention may be made by any
method. In some suitable methods, the starting materials are oil,
dispersant, optional surfactants, and cyclopropene complex. In some
embodiments, the cyclopropene complex starting material is in the
form of powder particles that contain cyclopropene complex, and the
powder particles have median size, as measured by the largest
dimension, much larger than 50 micrometer (for example, 200
micrometer or larger). In some embodiments, the starting materials
may be put into a media mill and then milled until the desired
particle size is obtained. In some embodiments, the milling process
is performed until the particles have median size, as measured by
the largest dimension, of 50 micrometer or smaller, or 20
micrometer or smaller, or 10 micrometer or smaller, or 5 micrometer
or smaller, or 2 micrometer or smaller.
[0083] In some embodiments involving milling, the mixture that is
milled contains cyclopropene complex powder in an amount, by weight
based on the weight of the mixture that is milled, of 2% or
greater; or 5% or greater; or 10% or greater; or 20% or greater.
Independently, in some embodiments involving milling, the mixture
that is milled contains cyclopropene complex powder in an amount,
by weight based on the weight of the mixture that is milled, of 60%
or lower; or 50% or lower.
[0084] In some embodiments involving milling, the mixture that is
milled contains dispersant in an amount, by weight based on the
weight of the mixture that is milled, of 0.02% or greater; or 0.05%
or greater; or 0.1% or greater; or 0.2% or greater; or 0.5% or
greater; or 1% or greater. Independently, in some embodiments
involving milling, the mixture that is milled contains dispersant
in an amount, by weight based on the weight of the mixture that is
milled, of 10% or lower; or 7% or lower; or 5% or lower.
[0085] In some embodiments involving milling, the mixture that is
milled contains surfactant in an amount, by weight based on the
weight of the mixture that is milled, of 0.2% or greater; or 0.5%
or greater; or 1% or greater. Independently in some embodiments
involving milling, the mixture that is milled contains surfactant
in an amount, by weight based on the weight of the mixture that is
milled, of 30% or lower; or 10% or lower; or 6% or lower. In some
embodiments involving milling, the mixture that is milled contains
no surfactant.
[0086] In some embodiments involving milling, the mixture that is
milled contains oil in an amount, by weight based on the weight of
the mixture that is milled, of 40% or greater; or 50% or greater.
Independently, in some embodiments involving milling, the mixture
that is milled contains oil in an amount, by weight based on the
weight of the mixture that is milled, of 98% or lower; or 80% or
lower; or 70% or lower.
[0087] In some embodiments involving milling, water is excluded
from the starting materials, from the mixture that is milled, and
from the milled mixture when it is stored. That is, in such
embodiments, the amount of water in the mixture of starting
materials, by weight based on the total weight of starting
materials, is 2% or less; or 1% or less; or 0.5% or less; or 0.2%
or less; or 0.1% or less; or zero. In such embodiments, the same
amounts of water are contemplated for the mixture during milling
and for the milled mixture when it is stored. The mixture during
storage may or may not have higher amount of water than the mixture
during milling. Independently, the mixture during milling may or
may not have higher amount of water than the mixture of starting
materials prior to milling.
[0088] The product of such a milling process may be used
immediately or may be stored.
[0089] When it is desired to practice a continuous oil embodiment,
the product of the milling process may be used directly, or further
oil may be added to the product of such a milling process.
[0090] When it is desired to practice a continuous water
embodiment, the product of such a milling process will be divided
into droplets and suspended in an aqueous medium. In some
embodiments, the product of the milling process may be added to the
aqueous medium and subjected to agitation, and the product of the
milling process will divide into suspended droplets. In some of
such embodiments, one or more surfactant is chosen to assist the
product of the milling process to divide and suspend in the aqueous
medium, and such surfactant or surfactants are added to the
starting materials and included in the mixture that is milled.
Whether or not surfactant is included in the mixture that is
milled, one or more surfactant may be added, after the milling
process is completed, to the product of the milling process, or to
the aqueous medium (before or after the aqueous medium is mixed
with the product of the milling process).
[0091] In general, whenever a cyclopropene complex is used, it is
known that direct contact between cyclopropene complex and water
sometimes causes release of cyclopropene from the complex earlier
than desired, and the cyclopropene may be lost (for example,
through diffusion out of the composition, through chemical
reaction, or a combination thereof). It is contemplated that, in
the practice of continuous water embodiments of the present
invention, the cyclopropene complex remains in the oil medium, so
that contact between the cyclopropene complex and water is
minimized or eliminated, and thus a desirably high fraction of the
cyclopropene molecules of the composition remain in the
composition.
[0092] One possible use for the composition of the present
invention is to treat plants or plant parts by bringing composition
of the present invention into contact with plants or plant parts.
Plants that produce useful plant parts are known herein as "crop
plants." Treatment may be performed on growing plants or on plant
parts that have been harvested from growing plants. It is
contemplated that, in performing the treatment on growing plants,
the composition of the present invention may be contacted with the
entire plant or may be contacted with one or more plant parts.
Plant parts include any part of a plant, including, for example,
flowers, buds, blooms, seeds, cuttings, roots, bulbs, fruits,
vegetables, leaves, and combinations thereof.
[0093] Removal of useful plant parts from crop plants is known as
harvesting. In some embodiments, crop plants are treated with
composition of the present invention prior to the harvesting of the
useful plant parts.
[0094] The composition of the present invention may be brought into
contact with plants or plant parts by any method, including, for
example, spraying, dipping, drenching, fogging, and combinations
thereof. In some embodiments, spraying is used.
[0095] Suitable treatments may be performed on plants that are
planted in a field, in a garden, in a building (such as, for
example, a greenhouse), or in another location. Suitable treatments
may be performed on a plants that are planted in open ground, in
one or more containers (such as, for example, a pot, planter, or
vase), in confined or raised beds, or in other places. In some
embodiments, treatment is performed on plants that are in a
location other than in a building. In some embodiments, plants are
treated while they are growing in containers: such as, for example,
pots, flats, or portable beds.
[0096] Many of the plants that are suitable for use in the practice
of the present invention can be usefully divided into categories or
groups. One useful method for defining such groups is the
"Definition and Classification of Commodities," published on or
before Mar. 23, 2006, by the Food and Agriculture Organization
("FAO") of the United Nations as a "Draft."
[0097] In the practice of some embodiments of the present
invention, it is contemplated to use plants that produce one or
more crops that fall within any one of the following crop
groups.
[0098] Crop Group 1 is cereals, including, for example, wheat,
rice, barley, corn, popcorn, rye, oats, millet, sorghum, buckwheat,
quiona, fonio, triticale, canary seed, canagua, quihuicha, adlay,
wild rice, and other cereals. In some embodiments of the present
invention, suitable plants are those that produce wheat or rice or
corn or sorghum. In some embodiments, corn plants are suitable. In
some embodiments, wheat plants are suitable. Crop Group 2 is roots
and tubers.
[0099] Crop Group 3 is sugar crops, including, for example, sugar
cane, sugar beet, sugar maple, sweet sorghum, sugar palm, and other
sugar crops. Crop Group 4 is pulses, including, for example, beans,
chickpea, garbanzo, blackeyed pea, pigeon pea, lentil, and other
pulses. Crop Group 5 is nuts, including, for example, brazil nuts,
cashew nuts, chestnuts, almonds, walnuts, pistachios, hazelnuts,
pecan nut, macadamia nut, and other nuts.
[0100] Crop Group 6 is oil-bearing crops, including, for example,
soybeans, groundnuts (including peanuts), coconuts, oil palm fruit,
olives, karite nuts, castor beans, sunflower seeds, rapeseed,
canola, tung nuts, safflower seed, sesame seed, mustard seed, poppy
seed, melonseed, tallowtree seeds, kapok fruit, seed cotton,
linseed, hempseed, and other oilseeds. In some embodiments, soybean
plants are suitable.
[0101] Crop Group 7 is vegetables, including, for example,
cabbages, artichokes, asparagus, lettuce, spinach, cassava leaves,
tomatoes, cauliflower, pumpkins, cucumbers and gherkins, eggplants,
chilies and peppers, green onions, dry onions, garlic, leek, other
alliaceous vegetables, green beans, green peas, green broad beans,
string beans, carrots, okra, green corn, mushrooms, watermelons,
cantaloupe melons, bamboo shoots, beets, chards, capers, cardoons,
celery, chervil, cress, fennel, horseradish, marjoram, oyster
plant, parsley, parsnips, radish, rhubarb, rutabaga, savory,
scorzonera, sorrel, watercress, and other vegetables.
[0102] Crop Group 8, is fruits, including, for example, bananas and
plantains; citrus fruits; pome fruits; stone fruits; berries;
grapes; tropical fruits; miscellaneous fruits; and other fruits.
Crop Group 9 is fibers, including, for example, cotton, flax, hemp,
kapok, jute, ramie, sisal, and other fibers from plants. In some
embodiments, cotton plants are suitable. Crop Group 10 is spices.
Crop Group 11 is Fodder crops. Fodder crops are crops that are
cultivated primarily for animal feed. Crop Group 12 is stimulant
crops, including, for example, coffee, cocoa bean, tea, mate, other
plants used for making infusions like tea, and other stimulant
corps.
[0103] Crop Group 13 is tobacco and rubber and other crops,
including, for example, plant oils used in perfumery, food, and
other industries, pyrethrum, tobacco, natural rubber, natural gums,
other resins, and vegetable waxes.
[0104] In some embodiments, the present invention involves
treatment of any non-citrus plant (i.e., any plant that is not in
the genus Citrus). In other embodiments, the practice of the
present invention is limited to the treatment of non-citrus plants.
Independently, in some embodiments, all the plants that are treated
are not members of the genus Nicotiana.
[0105] In some embodiments, the composition of the present
invention is used to treat crop plants growing in a field. Such a
treatment operation may be performed one time or more than one time
on a particular group of crop plants during a single growing
season. In some embodiments, the amount of cyclopropene used in one
treatment is 0.1 gram per hectare (g/ha) or more; or 0.5 g/ha or
more; or 1 g/ha or more; or 5 g/ha or more; or 25 g/ha or more; or
50 g/ha or more; or 100 g/ha or more. Independently, in some
embodiments, the amount of cyclopropene used in one spraying
operation is 6000 g/ha or less; or 3000 g/ha or less; or 1500 g/ha
or less.
[0106] Also contemplated are embodiments in which harvested plant
parts are treated.
[0107] In some embodiments, the composition of the present
invention includes one or more metal-complexing agents. A
metal-complexing agent is a compound that contains one or more
electron-donor atoms capable of forming coordinate bonds with a
metal atoms. Some metal-complexing agents are chelating agents. As
used herein, a "chelating agent" is a compound that contains two or
more electron-donor atoms that are capable of forming coordinate
bonds with a metal atom, and a single molecule of the chelating
agent is capable of forming two or more coordinate bonds with a
single metal atom. In some embodiments, one or more chelating agent
is used. In some embodiment, no metal-coordinating agent is used
that is not a chelating agent.
[0108] In embodiments in which one or more chelating agent is used,
suitable chelating agents include, for example, organic and
inorganic chelating agents. Among the suitable inorganic chelating
agents are, for example, phosphates such as, for example,
tetrasodium pyrophosphate, sodium tripolyphosphate, and
hexametaphosphoric acid. Among the suitable organic chelating
agents are those with macrocyclic structures and non-macrocyclic
structures.
[0109] Some suitable organic chelating agents that have
non-macrocyclic structures are, for example, aminocarboxylic acids,
1,3-diketones, hydroxycarboxylic acids, polyamines, aminoalcohols,
aromatic heterocyclic bases, phenol, aminophenols, oximes, Shiff
bases, sulfur compounds, and mixtures thereof. In some embodiments,
the chelating agent includes one or more aminocarboxylic acids, one
or more hydroxycarboxylic acids, one or more oximes, or a mixture
thereof. Some suitable aminocarboxylic acids include, for example,
ethylenediaminetetraacetic acid (EDTA),
hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic
acid (NTA), N-dihydroxyethylglycine (2-HxG),
ethylenebis(hydroxyphenylglycine) (EHPG), and mixtures thereof.
Some suitable hydroxycarboxylic acids include, for example,
tartaric acid, citric acid, gluconic acid, 5-sulfoslicylic acid,
and mixtures thereof. Some suitable oximes include, for example,
dimethylglyoxime, salicylaldoxime, and mixtures thereof. In some
embodiments, EDTA is used.
[0110] The use of metal-complexing agent in the present invention
is optional. In some continuous water embodiments, one or more
metal-complexing agent is used. In some continuous water
embodiments, no metal-complexing agent is used. In some continuous
oil embodiments, no metal-complexing agent is used.
[0111] It is to be understood that for purposes of the present
specification and claims that, unless specifically stated
otherwise, when a value is stated to be "from X to Y," it is meant
that that value is X or greater and also is Y or less.
[0112] It is to be understood that for purposes of the present
specification and claims that, unless specifically stated
otherwise, when a compound is described as a result of a particular
chemical reaction, such a description is intended to describe the
structure of the compound, whether or not the compound is actually
made by performing that particular chemical reaction. For example,
an "ethoxylate of a fatty alcohol" is a compound whose structure
can be understood by envisioning an ethoxylation process performed
on a fatty alcohol, and such a compound may be made by a process of
ethoxylation of a fatty alcohol or may be made by a different
process.
[0113] It is to be understood that for purposes of the present
specification and claims that, unless specifically stated
otherwise, operations are performed at 25.degree. C. at one
atmosphere of pressure in air.
[0114] It is to be understood that for purposes of the present
specification and claims that the range and ratio limits recited
herein can be combined. For example, if ranges of 60 to 120 and 80
to 110 are recited for a particular parameter, it is understood
that the ranges of 60 to 110 and 80 to 120 are also contemplated.
As a further, independent, example, if a particular parameter is
disclosed to have suitable minima of 1, 2, and 3, and if that
parameter is disclosed to have suitable maxima of 9 and 10, then
all the following ranges are contemplated: 1 to 9, 1 to 10, 2 to 9,
2 to 10, 3 to 9, and 3 to 10.
EXAMPLES
[0115] In the Examples below, the following materials were used:
[0116] Complex 1=Dry powder containing complex of 1-MCP and
alpha-cyclodextrin, contains 3.8% 1-MCP by weight. Median size,
measured by the longest dimension, is greater than 100 micrometer.
Median aspect ratio is over 50. [0117] Oil P1=paraffin oil
containing aryl alkyl ethoxylate surfactant, from Whitmire
Micro-Gen Company [0118] Oil P2=paraffin oil, from Petro Canada
Company [0119] Brij.TM. 30=surfactant: (ethylene oxide).sub.4
lauryl ether, from Croda (HLB 9.7) [0120] Silwet.TM.
L-77=surfactant: nonionic silicone from OSi Specialties (HLB 5 to
8) [0121] Atlox.TM. 4914=dispersant: block copolymer of
poly(ethylene oxide) and alkyd resin, from Croda (HLB 6) [0122]
EDTA=ethylenediamine tetraacetic acid, sodium salt [0123]
Atsurf.TM. 595=surfactant: glycol mono oleate from Croda Company
(HLB 3.8) [0124] Dyne-Amic.TM. oil=blend of highly refined
methylated vegetable oils in combination with organosilicone-based
surfactants from Helena Chemicals [0125] Oil Emulsion 1=0.38 parts
by weight Dyne-Amic.TM. oil added to 99.62 parts by weight water,
and agitated [0126] Rizo.TM. Oil=emulsifiable methylated soybean
oil, from Rizo bacter Company [0127] SoyGold.TM. 1100=methylated
soybean oil, from Ag Environmental Products Company
Example 1
Formation of Formulation B
[0128] The following ingredients were added to a media mill: [0129]
292.4 g of Oil P1 [0130] 102.0 g of Complex 1 [0131] 5.6 g of
Atlox.TM. 4914 The mixture of ingredients was processed in the
media mill until median particle size, as measured by the largest
dimension, was less than 2 micrometers.
Example 2
Formation of Formulation C
[0132] The following ingredients were added to a media mill: [0133]
194.2 g of Oil P2 [0134] 175.0 g of Complex 1 [0135] 6.0 g of
Brij.TM. 30 [0136] 18.0 g of Silwet.TM. L-77 [0137] 6.8 g of
Atlox.TM. 4914 The mixture of ingredients was processed in the
media mill until median particle size, as measured by the largest
dimension, was less than 2 micrometers.
Example 3
Formation of Formulation D
[0138] The following ingredients were added to a media mill: [0139]
200.4 g of SoyGold 1100 [0140] 180.0 g of Complex 1 [0141] 10.0 g
of Silwet.TM. L-77 [0142] 4.0 g of Atlox.TM. 4914 [0143] 5.6 g of
EDTA The mixture of ingredients was processed in the media mill
until median particle size, as measured by the largest dimension,
was less than 2 micrometers.
Example 4
Retention of 1-MCP
[0144] The ability of a formulation to retain 1-MCP was assessed by
spraying the spray mixture through a standard spray nozzle,
collecting the spray liquid at the spray nozzle and at 46 cm (18
inches) from the nozzle, and analyzing for 1-MCP by capturing the
collected liquid in a closed container and analyzing the headspace
gas by gas chromatography. Gas chromatography of the headspace was
performed as described in US Patent Publication 2005/0261132. The
initial and final unsprayed portion is also analyzed to determine
the amount lost to spraying and the amount lost to headspace during
the spraying operation.
[0145] Spray Formulation "Comparative SF-A4" was a mixture of Oil
Emulsion 1 and Complex 1. Spray Formulation "SF-B4" was Formulation
B, added to water. Each Spray formulation contained 100 mg/L 1-MCP
and was sprayed through TeeJet.TM. XR8002VS nozzles at 138 kPa (20
psi) pressure. The results are shown in Table 1:
TABLE-US-00001 TABLE 1 MCP concentration (% of concentration in
initial unsprayed formulation) final unsprayed Spray Composition at
nozzle 46 cm from nozzle portion Comparative SF-A1 58 33 75 SF-B 75
74 99
Table 1 shows that the oil formulation performs much better than
the tank mix of 1-MCP complex and oil and also helps keep the 1-MCP
in the unsprayed spray liquid.
Example 5
Biological Efficacy
[0146] Efficacy of formulations was assessed by spraying greenhouse
tomato plants, exposing them to ethylene, and evaluating the
resistance to epinastic (i.e., leaf bending/curling) response
specifically caused by ethylene.
[0147] The 1-MCP treated plants and the controls were placed into
an SLX controlled-atmosphere shipping box and sealed. To the box,
ethylene was injected through a septum, which gave a concentration
of 14 ppm. The plants were held sealed for 12-14 hours in the dark
with ethylene in the atmosphere. At the end of ethylene treatment,
the box was opened and scored for epinasty. The results are
reported as leaf angle relative to the stem wherein a value of 50
degrees is typical of an unaffected leaf and 120 degrees is one
fully bent by the action of ethylene.
[0148] Spray Formulation "Comparative SF-A51" was 99.99 parts by
weight of Oil Emulsion 1 plus 0.0132 parts by weight of Complex 1.
Comparative SF-A2 was sprayed on the plants to give a rate of 1 g
1-MCP/Ha. Spray Formulation "Comparative SF-A52" was 99.17 parts by
weight of Oil Emulsion 1 plus 0.132 parts by weight of Complex 1.
Comparative SF-A2 was sprayed on the plants to give a rate of 10 g
1-MCP/Ha.
[0149] Spray Formulation "SF-051" was 0.0279 parts by weight of
Formulation C plus 99.97 parts by weight of water. SF-051 was
sprayed on the plants to give a rate of 1 g 1-MCP/Ha. Spray
Formulation "SF-052" was 0.279 parts by weight of Formulation C
plus 99.72 parts by weight of water. SF-052 was sprayed on the
plants to give a rate of 10 g 1-MCP/Ha.
[0150] Results were as follows:
TABLE-US-00002 Composition 1-MCP g/Ha Leaf Angle untreated,
unexposed to ethylene 0 52.degree. Oil Emulsion 1 0 116.degree.
water 0 116.degree. Comparative SF-A51 1 119.degree. SF-C51 1
87.degree. Comparative SF-A52 10 82.degree. SF-C52 10 54.degree.
Leaf angles demonstrate that the oil formulations SF-C51 and SF-C52
are more effective at counteracting the effects of ethylene than
the comparative formulations.
Example 6
Crop Yield Increase
[0151] Efficacy of formulations was assessed in field applications
on soybeans. The measure of efficacy was yield increase.
[0152] Spray Formulation "Comparative SF-A6" was made as follows.
98.97 parts by weight of water was mixed in the spray tank with 1
part by weight of Rizo.TM. Oil, and then 0.0329 parts by weight of
Complex 1 was mixed with the mixture in the spray tank. The
spraying rate was chosen to give 25 g 1-MCP/Ha in 200 L/Ha water
containing 2 L/Ha of Rizo.TM. Oil. Comparative SF-A6 was applied by
ground-level spray.
[0153] Sprayable Formulation SF-D6 was made by mixing 1.25 liter of
Formulation D with 3.75 liter of Rizo.TM. Oil. Sprayable
Formulation SF-D6 was applied by aerial spraying at rate of 25 g
1-MCP/Ha in 5 L total oil/Ha. Note: no water was used in SF-D6, so
the total liquid spray volume was 5 L/Ha.
[0154] Results were as follows. Yield is reported as a percentage
of the yield obtained from the untreated control.
TABLE-US-00003 Spray Treatment Soybean Yield Comparative SF-A6 103%
SF-D6 110% SF-D6 increased soybean yield significantly more than
the Comparative formulation.
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