EP2903433A2 - Oil formulations with thickeners - Google Patents
Oil formulations with thickenersInfo
- Publication number
- EP2903433A2 EP2903433A2 EP13843946.8A EP13843946A EP2903433A2 EP 2903433 A2 EP2903433 A2 EP 2903433A2 EP 13843946 A EP13843946 A EP 13843946A EP 2903433 A2 EP2903433 A2 EP 2903433A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- weight
- oil
- cyclopropene
- thickener
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
Definitions
- the cyclopropene is often in the form of a complex with a molecular encapsulating agent.
- 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.
- such treatment of plant parts can sometimes desirably delay unwanted ripening.
- such treatment of crop plants prior to harvest can sometimes improve the yield of the crop.
- US 6,313,068 discloses grinding and milling of dried powder of a complex of cyclodextrin and methylcyclopropene.
- 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.
- This invention is based on unexpected effect of at least one thickener to maintain suspension or dispersion of solid particles in an oil medium.
- Such effect of thickener enables significant higher weight ratio of solid particles in such suspension composition as compared to previously known compositions.
- the suspension compositions provided herein enable more active ingredient in the solid particle to be present in a fixed volume or weight of such composition as compared to previously known compositions.
- One advantage of the suspension composition provided herein can be for aerial spraying of active ingredient such as herbicides, insecticides, or growth regulating compounds.
- Other advantages of the suspension composition provided herein include slow release of cyclopropene, and lower payload weight for airplanes and helicopters for aerial applications.
- suspension of cyclopropene/cyclodextrin complexes in a hydrophobic fluid with adjuvants which can form a system for the controlled delivery of cyclopropenes.
- composition comprising an oil medium and at least one thickener, wherein the composition is a suspension of solid particles in the oil medium, and the solid particles comprise cyclopropene and molecular encapsulating agent.
- the suspension does not settle for at least two weeks, at least four weeks, at least eight weeks, at least twenty weeks, or at least forty weeks.
- the oil medium is selected from the group consisting of white mineral oil, hydrotreated middle petroleum distillate, hydrotreated light petroleum distillate, and
- the cycloprop d is of the formula:
- R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
- R is C 1-8 alkyl. In another embodiment, R is methyl.
- the cyclopropene compound is of the formula:
- R 1 is a substituted or unsubstituted C C 4 alkyl, C C 4 alkenyl, C C 4 alkynyl, C C 4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
- the cyclopropene comprises 1-methylcyclopropene (1-MCP).
- the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, and combinations thereof.
- the molecular encapsulating agent comprises alpha-cyclodextrin.
- the solid particles comprise at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% by weight of the composition.
- the solid particles comprise 10-20%, 10-30%, 10-40%, 10-50%, 10-60%, 20-40%, 30-60%, or 40-60% by weight of the composition.
- the composition comprises at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% by weight of a complex of 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin.
- the polymeric thickener comprises at least one component selected from the group consisting of polypropylene, polyisoprene, polybutadiene, poly(styrene-butadiene), poly(styrene-ethylene/propylene), poly(ethylene-propylene-diene), polyurethane, polymethacrylate, polyisobutylene, poly(isobutylene-succinic acid),
- the polymeric thickener comprises a first component and a second component, with the first component having a higher weight average molecular weight than the second component.
- the weight ratio of the first component to the second component is at least 1:5, at least 1: 10, at least 1:20, at least 1:30, at least 1:40, or at least 1:50.
- the weight ratio of the first component to the second component is between 1:5 and 1:20; between 1: 10 to 1:40, or between 1:5 and 1:50.
- the polymeric thickener does not comprise ethylene propylene norbornadiene copolymer. In a further embodiment, such ethylene propylene norbornadiene copolymer does not comprise Nordel IP3745P. In another embodiment, the polymeric thickener does not comprise styrene ethylene/propylene copolymer. In a further embodiment, such styrene ethylene/propylene copolymer does not comprise Septon 1020 or Septon 1001.
- a method of preparing a suspension composition comprising (a) placing materials comprising complex comprising cyclopropene and molecular encapsulating agent, an oil medium, and at least one thickener into a media mill; and (b) milling the materials into a composition comprising solid particles.
- the suspension composition does not settle for at least two weeks, at least four weeks, at least eight weeks, at least twenty weeks, or at least forty weeks.
- the oil medium is selected from the group consisting of white mineral oil, hydrotreated middle petroleum distillate, hydrotreated light petroleum distillate, and combinations thereof.
- the white mineral oil comprises Blandol and/or Klearol.
- the hydrotreated middle petroleum distillate comprises Conosol 260, Unipar SH 260 CC, and/or Isopar V.
- the hydrotreated light petroleum distillate comprises Unipar SH 210 AS and/or Isopar M.
- the cycloprop d is of the formula:
- R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
- R is Ci_8 alkyl. In another embodiment, R is methyl.
- the cyclopropene compound is of the formula:
- R 1 is a substituted or unsubstituted C C 4 alkyl, C C 4 alkenyl, C C 4 alkynyl, C C 4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
- the cyclopropene comprises 1-methylcyclopropene (1-MCP).
- the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, and combinations thereof.
- the molecular encapsulating agent comprises alpha-cyclodextrin.
- the composition comprises at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% by weight a complex of 1- methylcyclopropene (1-MCP) and alpha-cyclodextrin.
- the composition comprises 10-20%, 10-30%, 10-40%, 10-50%, 10-60%, 20-40%, 30-60%, or 40-60% by weight a complex of 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin.
- the polymeric thickener comprises at least one component selected from the group consisting of polypropylene, polyisoprene, polybutadiene, poly(styrene-butadiene), poly(styrene-ethylene/propylene), poly(ethylene-propylene-diene), polyurethane, polymethacrylate, polyisobutylene, poly(isobutylene-succinic acid),
- the polymeric thickener comprises a first component and a second component, with the first component having a higher weight average molecular weight than the second component.
- the weight ratio of the first component to the second component is at least 1:5, at least 1: 10, at least 1:20, at least 1:30, at least 1:40, or at least 1:50.
- the weight ratio of the first component to the second component is between 1:5 and 1:20; between 1: 10 to 1:40, or between 1:5 and 1:50.
- the polymeric thickener does not comprise ethylene propylene norbornadiene copolymer.
- such ethylene propylene norbornadiene copolymer does not comprise Nordel IP3745P.
- the polymeric thickener does not comprise styrene ethylene/propylene copolymer.
- such styrene ethylene/propylene copolymer does not comprise Septon 1020 or Septon 1001.
- cyclopropene compound is any compound with the formula
- 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 1 , R 2 , R 3 and R 4 ) the total number of heteroatoms (i.e., atoms that are neither H nor C) is from 0 to 6.
- 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.
- the R 1 , R 2 , R 3 , and R 4 groups are independently selected from the suitable groups.
- the R 1 , R 2 , R 3 , and R 4 groups may be the same as each other, or any number of them may be different from the others.
- R 3 , and R 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 1 , R 2 , R 3 , and R 4 may be substituted or unsubstituted.
- groups that are suitable for use as one or more of R 1 , R 2 , R 3 , and R 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.
- R 1 , R 2 , R 3 , and R 4 groups are, for example, aliphatic groups.
- suitable aliphatic groups include, for example, alkyl, alkenyl, and alkynyl groups.
- Suitable aliphatic groups may be linear, branched, cyclic, or a combination thereof.
- suitable aliphatic groups may be substituted or unsubstituted.
- 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
- 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
- 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.
- R 1 , R 2 , R 3 , and R 4 groups are, for example, substituted and unsubstituted aliphatic-oxy groups, such as, for example, alkenoxy, alkoxy, alkynoxy, and alkoxycarbonyloxy.
- R 1 , R 2 , R 3 , and R 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 dialkylamino sulfonyl.
- R 1 , R 2 , R 3 , and R 4 groups are, for example, substituted and unsubstituted cycloalkylsulfonyl groups and cycloalkylamino groups, such as, for example, dicycloalkylaminosulfonyl and dicycloalkylamino.
- R 1 , R 2 , R 3 , and R 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).
- R 2", R 3 J , and R 4" groups are heterocyclyloxy, heterocyclylcarbonyl, diheterocyclylamino, and diheterocyclylaminosulfonyl.
- R 1 , R 2 , R 3 , and R 4 groups are, for example, substituted and unsubstituted aryl groups.
- Suitable substituents are those described herein above.
- 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, arylamino sulfonyl, and haloalkylthio.
- R 1 , R 2 , R 3 , and R 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 1 , R 2 , R 3 , and R 4 groups are diheteroarylamino, heteroarylthioalkyl, and diheteroarylaminosulfonyl.
- R 1 , R 2 , R 3 , and R 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.
- 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.
- heterocyclic G groups some suitable heteroatoms are, for example, nitrogen, sulfur, oxygen, and combinations thereof.
- Ring systems 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).
- G is a ring system that contains a saturated or unsaturated 3 membered ring, such as, for example, a substituted or unsubstituted cyclopropane,
- G is a ring system that contains a 4 membered heterocyclic ring; in some of such embodiments, the heterocyclic ring contains exactly one heteroatom.
- 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.
- 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.
- each G is independently a substituted or unsubstituted phenyl, pyridyl, cyclohexyl, cyclopentyl, cycloheptyl, pyrolyl, furyl, thiophenyl, triazolyl, pyrazolyl, 1,3-dioxolanyl, or morpholinyl.
- G is unsubstituted or substituted phenyl, cyclopentyl, cycloheptyl, or cyclohexyl.
- G is cyclopentyl, cycloheptyl, cyclohexyl, phenyl, or substituted phenyl.
- G is substituted phenyl.
- embodiments in which G is substituted phenyl are embodiments, for example, in which there may be 1, 2, or 3 substituents.
- R 3 and R 4 are combined into a single group, which is attached to the number 3 carbon atom of the cyclopropene ring by a double bond.
- one or more of R 1 , R 2 , R 3 , and R 4 is a structure that has no double bond. Independently, in some embodiments, one or more of R 1 , R 2 , R 3 , and R 4 is a structure that has no triple bond. Independently, in some embodiments, one or more R 2", R 3 , and R 4 is a structure that has no halogen atom substituent. Independently, in some embodiments, one or more of R 1 , R 2 , R 3 , and R 4 is a structure that has no substituent that is ionic.
- one or more of R 1 , R 2 , R 3 , and R 4 is hydrogen or (Ci-Cio) alkyl. In some embodiments, each of R 1 , R 2 , R 3 , and R 4 is hydrogen or (C Cg) alkyl. In some embodiments, each of R 1 , R 2 , R 3 , and R 4 is hydrogen or (Ci-C 4 ) alkyl. In some embodiments, each of R 1 , R 2 , R 3 , and R 4 is hydrogen or methyl. In some embodiments, R 1 is (C C 4 ) alkyl and each of R 2 , R 3 , and R 4 is hydrogen. In some embodiments, R 1 is methyl and each of R 2 , R 3 , and R 4 is hydrogen. In some embodiments, R 1 is methyl and each of R 2 , R 3 , and R 4 is hydrogen, and the cyclopropene compound is known herein as 1- methylcycplopropene or "1-MCP.”
- a cyclopropene is used that has boiling point at one atmosphere pressure of 50°C or lower; or 25°C or lower; or 15°C or lower.
- a cyclopropene is used that has boiling point at one atmosphere pressure of -100°C or higher; -50°C or higher; or -25°C or higher; or 0°C or higher.
- 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. Patents No. 5,518,988 and 6,017,849.
- the composition of the present invention may include at least one molecular encapsulating agent.
- 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.”
- At least one cyclopropene complex is present that is an inclusion complex.
- the molecular encapsulating agent forms a cavity, and the cyclopropene or a portion of the cyclopropene is located within that cavity.
- 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.
- 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.
- the cyclopropene molecular encapsulation agent complexes can be prepared by any means.
- 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. Patent No. 6,017,849.
- 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.
- 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.
- the amount of molecular encapsulating agent can usefully be characterized by the ratio of moles of molecular encapsulating agent to moles of cyclopropene.
- the ratio of moles of molecular encapsulating agent to moles of cyclopropene may be 0.1 or larger; 0.2 or larger; 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 may be 2 or lower; or 1.5 or lower.
- 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.
- 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.
- 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, MI or Cerestar USA,
- oils are used.
- an “oil” is a compound that is liquid at 25 °C and 1 atmosphere pressure and that has a boiling point at 1 atmosphere pressure of 30°C or higher.
- oil does not include water, does not include surfactants (as described herein), and does not include dispersants (as described herein).
- one or more oil may be used that has boiling point of 50 °C or higher; or 75 °C or higher; or 100 °C or higher. In some embodiments, every oil that is used has boiling point of 50°C or higher. In some embodiments, every oil that is used has boiling point of 75 °C or higher. In some embodiments, every oil that is used has boiling point of 100°C or higher.
- 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.
- 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).
- 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.
- 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.
- suitable hydrocarbon oils include, for example, hexane, decane, dodecane, hexadecane, diesel oil, hydro treated light petroleum distillates, hydrotreated medium petroleum distillates, refined paraffinic oil (e.g., Ultrafine spray oil from Sun Company), and mixtures thereof. In some embodiments, every oil that is used is a hydrocarbon oil.
- 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, which 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.
- esters of fatty acids 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.
- 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.
- 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.
- a suitable triglyceride is soybean oil.
- Suitable fatty non-hydrocarbon oils may be synthetic or natural or modifications of natural oils or a combination or mixture thereof.
- suitable modifications of natural oils are, for example, alkylation, hydrogenation, hydroxylation, alkyl hydroxylation, alcoholysis, hydrolysis, epoxidation, halogenation, sulfonation, oxidation, polymerization, and combinations thereof.
- alkylated (including, for example, methylated and ethylated) oils are used.
- One suitable modified natural oil is methylated soybean oil.
- Also among the suitable fatty non-hydrocarbon oils are self-emulsifying esters of fatty acids.
- silicone oils 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
- Silicone oils include, for example, polydimethylsiloxane oils.
- Polydimethylsiloxane oils are oligomers or polymers that contain units of the form
- XI C3 ⁇ 4.
- XI 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.
- every oil that is used is a silicone oil.
- all XI groups are groups that are not hydrophilic. In some suitable polydimethylsiloxane oils, all XI groups are alkyl groups. In some suitable polydimethylsiloxane oils, all XI groups are methyl. In some embodiments, every silicone oil is a polydimethylsiloxane oil in which all XI groups are methyl. In some suitable polydimethylsiloxanes, at least one unit has an XI group that is not methyl; if more than one non-methyl XI unit is present, the non-methyl XI units may be the same as each other, or two or more different non-methyl XI 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. Mixtures of suitable oils are also suitable.
- 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.
- sustained 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 °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 or float to the top of the container.
- 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.
- suspensions are used that are stable upon storage for 2 days or longer, or 5 days or longer, or 10 days or longer.
- the collection of particles can be 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.
- 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
- 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.
- 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.
- 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.
- 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.”
- the particles that are suspended in the oil medium may contain cyclopropene and molecular encapsulating agent.
- 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.
- 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 may be 80% or more; or 90% or more; or 95% or more; or 99% or more.
- 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.
- a "dispersant” is a compound that is capable of assisting a solid particle to form a stable suspension in a liquid medium. Most dispersants act by minimizing the ability of the particles to agglomerate making, essentially, larger particles which are more likely to settle (or cream).
- 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.
- 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.
- hydrophilic group 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.
- the groups may be attached to the dispersant molecule in any way.
- 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.
- 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.
- HLB value One useful characteristic of a nonionic molecule is the HLB value, which is defined by the equation
- M H is the molecular mass of the hydrophilic portion of the molecule
- M is the molecular mass of the molecule
- a molecule of interest 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.
- acid value is the milligrams of KOH needed to neutralize the molecule of interest, per gram of the molecule of interest.
- ASTM D-7253 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.
- one or more of the dispersants has HLB of higher than 4, or HLB of 5 or higher.
- one or more dispersant is used that has HLB of lower than 8, or HLB of 7 or lower.
- every dispersant that is used has HLB that is 5 to 7.
- 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.
- 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.
- every dispersant that is used has acid number that is 6 to 8 mg KOH / g.
- 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.
- 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.
- anionic surfactant in embodiments in which one or more anionic surfactant is used, some suitable anionic surfactants include, for example, the sulfo succinates (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.
- some suitable cationic surfactants include, for example, amine surfactants and quaternary ammonium salt surfactants. In some embodiments, no cationic surfactant is used.
- one or more nonionic surfactant is used.
- nonionic surfactants include, for example, fatty ethoxylates, fatty acid esters of polyhydroxy compounds, amide oxides, alkyl oxide block copolymers, silicone based nonionic surfactants,
- fluoro surfactants and mixtures thereof.
- 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.
- one or more fatty ethoxylate is used that is an aryl alkyl ethoxylate, a fatty alcohol ethoxylate, or a mixture thereof.
- Suitable silicone based nonionic surfactants include, for example, those with the formula
- n 1 to 5
- m 0 to 4
- Q is -(CH 2 ⁇ OCH 2 CH 2 ⁇ -OCH 3 where p is 1 to 6, and q is 3 to 20.
- n is 1.
- m is zero.
- p is 3.
- q is 7 or 8 or a mixture thereof.
- a suitable nonionic surfactant is Atplus 595. Mixtures of suitable surfactants are also suitable.
- Nonionic surfactants may be usefully characterized by HLB, as defined herein above.
- one or more nonionic surfactant is used that has HLB of 3 to 4.
- one or more nonionic surfactant is used that has HLB of 8 to 10.
- 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.
- the continuous medium of the composition of the present invention is the oil medium in which the particles are suspended.
- one or more surfactant is present in the composition.
- no surfactant is present in the composition.
- 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.
- 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.
- 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.
- 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.
- one or more surfactant is present in the composition.
- one or more nonionic surfactant is present in the composition.
- 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.
- 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.
- 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.
- the amount of cyclopropene, by weight based on the weight of the composition is 500 ppm or lower; or 200 ppm or lower.
- 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.
- 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.
- 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.
- 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.
- composition of the present invention may be made by any method.
- the starting materials are oil, dispersant, optional surfactants, and
- 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).
- the starting materials may be put into a media mill and then milled until the desired particle size is obtained.
- 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.
- 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.
- 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.
- 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 .05% or greater; or 0.1% or greater; or 0.2% or greater; or 0.5% or greater; or 1% or greater.
- 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.
- 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.
- 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.
- the mixture that is milled contains no surfactant.
- 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.
- 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.
- 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.
- the product of such a milling process may be used immediately or may be stored.
- the product of the milling process may be used directly, or further oil may be added to the product of such a milling process.
- the product of such a milling process will be divided into droplets and suspended in an aqueous medium.
- 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.
- 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.
- 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).
- 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.
- Removal of useful plant parts from crop plants is known as harvesting.
- crop plants are treated with composition of the present invention prior to the harvesting of the useful plant parts.
- 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.
- 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.
- 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.
- suitable plants are those that produce wheat or rice or corn or sorghum.
- corn plants are suitable.
- wheat plants are suitable.
- Crop Group 2 is roots and tubers.
- 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.
- 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.
- soybean plants are suitable.
- 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.
- 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.
- 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.
- the present invention involves treatment of any non-citrus plant (i.e., any plant that is not in the genus Citrus).
- the practice of the present invention is limited to the treatment of non-citrus plants.
- all the plants that are treated are not members of the genus Nicotiana.
- 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.
- 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.
- 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. Also contemplated are embodiments in which harvested plant parts are treated.
- 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.
- 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.
- one or more chelating agent is used.
- no metal-coordinating agent is used that is not a chelating agent.
- suitable chelating agents include, for example, organic and inorganic chelating agents.
- suitable inorganic chelating agents are, for example, phosphates such as, for example, tetrasodium pyrophosphate, sodium tripolyphosphate, and hexametaphosphoric acid.
- suitable organic chelating agents are those with macrocyclic structures and non-macrocyclic structures.
- 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.
- 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,
- EDTA ethylenediaminetetraacetic acid
- HEDTA hydroxyethylethylenediaminetriacetic acid
- NTA nitrilotriacetic acid
- 2-HxG N-dihydroxyethylglycine
- EHPG ethylenebis(hydroxyphenylglycine)
- 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.
- EDTA is used.
- 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.
- 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.
- Thickeners that can be incorporated into the suspension compositions provided include those components that thicken or increase viscosity of the composition.
- Thickeners that can be used in the suspension compositions provided include those components referred to in the art as viscosity controlling agents.
- thickeners examples include cellulose-based thickeners, for example
- thickeners include cellulose gum, alkane triols; acrylates; substituted celluloses such as hydroxy ethyl cellulose, carboxymethyl cellulose, methylcellulose, and hydroxypropyl cellulose; cetyl alcohol; gums such as natural gums or synthetic gums; long chain alcohols such as those having about 9 to about 24 carbon atoms; polyglycols such as polyethylene glycols, polypropylene glycols, polybutylene glycols, polyethylene propylene glycols, or mixtures thereof; waxes such as natural waxes or synthetic waxes; hydrogenated oils; glycol esters; fatty acid esters; long chain acids; acid amides; silicates; and mixtures thereof.
- thickeners include cellulose gum, alkane triols; acrylates; substituted celluloses such as hydroxy ethyl cellulose, carboxymethyl cellulose, methylcellulose, and hydroxypropyl cellulose; cetyl alcohol; gums such as natural gums or synthetic gums
- organoclays which can be made from natural smectite, hectorite or montmorillonite clays by reacting the hydrophilic clay with quaternary ammonium compounds, so that it becomes organophilic and therefore compatible with nonaqueous media.
- suitable thickeners include polymeric thickener which is an addition polymer of unsaturated carboxylic acids and/or anhydrides.
- polymeric thickeners include polyacrylates, polyalkylacrylates, polymethacrylate, and maleic anhydride. These polymeric thickeners may have an average molecular weight range from about 500,000 to about 2 millions; or 1 million to 4 millions.
- Suitable polymeric thickener can be selected from the group consisting of natural rubber, polypropylene, polyisoprene, polybutadiene, poly(styrene -butadiene), poly(ethylene- propylene-diene), polyurethane, polymethacrylate, polyisobutylene, poly(isobutylene-succinic acid), poly(isobutylene- succinic acid-polyacrylamide), polyurea and polyethylene.
- the polymeric thickener comprises a first component and a second component, with the first component having a higher weight average molecular weight than the second component.
- the polymeric thickener comprises a high molecular weight component comprising a (co- or homo-)polymer of propylene with a weight average molecular weight of at least 200.000, or 200.000-350.000, and a low molecular weight component comprising a (co- or homo-) polymer of propylene with a weight average molecular weight of less than 100.000, or 50.000-100.000.
- the weight ratio between the high molecular weight component and the low molecular weight component in the polymeric thickener can be 1:40 - 3: 1; 1:40 - 1: 1; 1:40 - 1:5; 1:25 - 1: 15; or 1: 18 - 1:20.
- the low molecular weight component comprises a
- the low molecular weight component comprises a polypropylene homopolymer.
- the high molecular weight component has a melt flow rate (ASTM D-1238) of 1.5-15; 1.5-7; or 3-5.
- the high molecular weight component comprises a polypropylene homopolymer or 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.
- said oil medium comprises one or more dispersant. In another embodiment, said oil medium comprises one or more nonionic surfactant. In another embodiment, 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. In another embodiment, said oil medium is in the form of droplets suspended in water. In another embodiment, said oil medium forms the continuous medium of said composition. In another embodiment, said particle have median aspect ratio of 20 or less.
- a process for treating plants or plant parts comprising contacting the composition provided herein with said plants or plant parts.
- a process for forming a composition 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 300 micrometer or less, of 200 micrometer or less, or of 50 micrometer or less.
- compositions comprising solid particles of a cyclopropene complex comprising a cyclopropene molecular or a portion of a cyclopropene molecular encapsulated in a molecular encapsulating agent, characterized in that said composition additionally comprises an oil medium that said solid particles are suspended in said oil medium, and that said solid particles have a median size, as measured by the largest dimension, of 50 micrometer or less.
- said oil medium comprises one or more dispersant.
- said molecular encapsulating agent is alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or a mixture thereof.
- said cyclopropene molecule has a structure of formula
- R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.
- R is Ci_8 alkyl. In another embodiment, R is methyl.
- said cyclopropene molecule has a structure of formula:
- R is a substituted or unsubstituted C C 4 alkyl, C C 4 alkenyl, C C 4 alkynyl, C C 4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
- the cyclopropene comprises 1-methylcyclopropene (1-MCP).
- said oil medium comprises one or more nonionic surfactant.
- 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.
- said oil medium is in the form of droplets suspended in water.
- said oil medium forms the continuous medium of said composition.
- said particle have median aspect ratio of 20 or less.
- 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.
- Oil PI paraffin oil containing aryl alkyl ethoxylate surfactant, from Whitmire Micro-Gen Company
- Oil P2 paraffin oil, from Petro Canada Company
- BrijTM 30 surfactant: (ethylene oxide) 4 lauryl ether, from Croda (HLB 9.7)
- SilwetTM L-77 surfactant: nonionic silicone from OSi Specialties (HLB 5 to 8)
- AtloxTM 4914 dispersant: block copolymer of poly(ethylene oxide) and alkyd resin, from
- EDTA ethylenediamine tetraacetic acid, sodium salt
- AtsurfTM 595 surfactant: glycol mono oleate from Croda Company (HLB 3.8)
- Dyne-AmicTM oil blend of highly refined methylated vegetable oils in combination with
- organosilicone-based surfactants from Helena Chemicals
- Oil Emulsion 1 0.38 parts by weight Dyne-AmicTM oil added to 99.62 parts by weight water, and agitated
- RizoTM Oil emulsifiable methylated soybean oil, from Rizo bacter Company
- SoyGoldTM 1100 methylated soybean oil, from Ag Environmental Products Company
- AtloxTM 4914 5.6 g of AtloxTM 4914 [00145] 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.
- 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.
- 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.
- 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.
- Spray Formulation "Comparative SF-A4" was a mixture of Oil Emulsion 1 and
- Spray Formulation "SF-B4" was Formulation B, added to water. Each Spray formulation contained lOOmg/L 1-MCP and was sprayed through TeeJetTM XR8002VS nozzles at 138 kPa (20 psi) pressure. The results are shown in Table 1:
- 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.
- 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.
- 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.
- Spray Formulation ""SF-C51” was 0.0279 parts by weight of Formulation C plus 99.97 parts by weight of water. SF-C51 was sprayed on the plants to give a rate of 1 g 1-MCP /Ha.
- Spray Formulation "SF-C52” was 0.279 parts by weight of Formulation C plus 99.72 parts by weight of water. SF-C52 was sprayed on the plants to give a rate of 10 g 1-MCP /Ha.
- Oil Emulsion 1 0 116° water 0 116°
- 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 RizoTM 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 25g 1-MCP/Ha in 200 L/Ha water containing 2 L/Ha of RizoTM Oil. Comparative SF-A6 was applied by ground-level spray.
- Sprayable Formulation SF-D6 was made by mixing 1.25 liter of Formulation D with 3.75 liter of RizoTM Oil. Sprayable Formulation SF-D6 was applied by aerial spraying at rate of 25g 1-MCP/Ha in 5 L total oil/Ha. Note: no water was used in SF-D6, so the total liquid spray volume was 5L/Ha. Results are shown in Table 3. Yield is reported as a percentage of the yield obtained from the untreated control.
- Kraton G1702H is a linear styrene ethylene/propylene diblock copolymer. 100 g of Kraton G1702H is mixed with 1900 g of Isopar V and heated with stirring to 100 °C for 30 minutes. A clear viscous liquid is formed with 5% solids.
- compositions can yield solutions with increased viscosity. Vegetable oils, including soybean oil and corn oil, do not exhibit this effect. When 1-methylcyclopropene / a-cyclodextrin complex and/or zeolite / molecular sieve are suspended in the thickened hydrocarbons, little or no settling occurs if the concentration of Kraton G1702H is greater than 2.0% by weight.
- a suspension of 10 % by weight of 1-methylcyclopropene / a-cyclodextrin complex and 3.3% by weight of Siliporite NK10AP (4A molecular sieve) in 2.25% Kraton G1702H is directly sprayable using traditional spray nozzles (Spraying Systems TeeJet XR8002 or XR8008) using a normal pressure of 30 psig to 60 psig.
- Polymers not suitable as thickeners include: (1) Nordel IP3745P - an ethylene propylene norbornadiene terpolymer: 100 g of Nordel IP3745 is mixed with 1900 g of Isopar V and heated, with stirring, to 100 °C for 4 hours. None seems to dissolve and no thickening is noted; (2) Septon 1020 - a linear styrene ethylene/propylene diblock copolymer: 100 g of Septon 1020 is mixed with 1900 g of Isopar V and heated, with stirring, to 100 °C for 4 hours.
- Septon 1001 - a linear styrene ethylene/propylene diblock copolymer 100 g of Septon 1001 is mixed with 1900 g of Isopar V and heated, with stirring, to 100 °C for 4 hours. Only a little dissolved but some (but insufficient) thickening is noted.
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Abstract
Description
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US201261710019P | 2012-10-05 | 2012-10-05 | |
PCT/US2013/059201 WO2014055208A2 (en) | 2012-10-05 | 2013-09-11 | Oil formulations with thickeners |
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EP2903433A4 EP2903433A4 (en) | 2016-04-20 |
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JP (1) | JP2015530474A (en) |
KR (1) | KR20150065792A (en) |
CN (1) | CN104837341B (en) |
AU (1) | AU2013325149B2 (en) |
BR (1) | BR112015007339A2 (en) |
CA (1) | CA2886520A1 (en) |
CL (1) | CL2015000847A1 (en) |
CR (1) | CR20150220A (en) |
IL (1) | IL238065B (en) |
IN (1) | IN2015DN02680A (en) |
MX (1) | MX2015004104A (en) |
NZ (1) | NZ706334A (en) |
PH (1) | PH12015500717A1 (en) |
RU (1) | RU2015116683A (en) |
SG (1) | SG11201502387QA (en) |
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US9012515B2 (en) | 2007-08-03 | 2015-04-21 | Rohm And Haas Company | Oil formulations with thickeners |
CN108703139B (en) * | 2018-06-28 | 2019-08-20 | 中国农业大学 | For preventing the oil-suspending agent and its preparation method and application of fruit shedding |
CN112314616A (en) * | 2020-11-10 | 2021-02-05 | 惠乾科技(广东)有限公司 | Microcapsule structure thickener, synthetic method thereof and application thereof in oil suspending agent |
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WO1997009882A1 (en) * | 1995-09-14 | 1997-03-20 | Valent U.S.A. Corporation | Phosphoroamidothioate coated sand and method |
US6017849A (en) * | 1998-08-20 | 2000-01-25 | Biotechnologies For Horticulture, Inc. | Synthesis methods, complexes and delivery methods for the safe and convenient storage, transport and application of compounds for inhibiting the ethylene response in plants |
US7101928B1 (en) * | 1999-09-17 | 2006-09-05 | Landec Corporation | Polymeric thickeners for oil-containing compositions |
US6953540B2 (en) * | 2000-09-29 | 2005-10-11 | Rohm And Haas Company | Continuous process for the preparation of encapsulated cyclopropenes |
US20030083209A1 (en) * | 2001-10-22 | 2003-05-01 | Moodycliffe Timothy I. | Viscosity modification of petroleum distillates |
TW200538037A (en) * | 2004-05-19 | 2005-12-01 | Rohm & Haas | Compositions with cyclopropenes and adjuvants |
CA2565427A1 (en) * | 2005-11-08 | 2007-05-08 | Rohm And Haas Company | Compositions with cyclopropenes and non-hydrocarbon oils |
US20070117720A1 (en) * | 2005-11-18 | 2007-05-24 | Jacobson Richard M | Compositions with cyclopropenes |
BRPI0806751B1 (en) * | 2007-01-17 | 2018-08-14 | Agrofresh Inc. | RELEASE OF ETHYLENE LOCKING AND / OR PROMOTION AGENTS |
JP5128392B2 (en) * | 2007-08-03 | 2013-01-23 | ローム アンド ハース カンパニー | Oil blend |
AU2010203673B2 (en) * | 2009-01-09 | 2015-04-09 | Syngenta Participations Ag | Stabilized agrochemical composition |
WO2011109144A1 (en) * | 2010-03-01 | 2011-09-09 | Rohm And Haas Company | Oil formulations comprising cylcopropene compounds |
US10206389B2 (en) * | 2010-06-07 | 2019-02-19 | Syngenta Participations Ag | Cyclopropene compositions |
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- 2013-09-11 EP EP13843946.8A patent/EP2903433A4/en not_active Withdrawn
- 2013-09-11 CN CN201380063258.XA patent/CN104837341B/en not_active Expired - Fee Related
- 2013-09-11 AU AU2013325149A patent/AU2013325149B2/en not_active Ceased
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CA2886520A1 (en) | 2014-04-10 |
CN104837341A (en) | 2015-08-12 |
MX2015004104A (en) | 2015-12-01 |
IN2015DN02680A (en) | 2015-09-04 |
CN104837341B (en) | 2018-05-25 |
WO2014055208A3 (en) | 2014-06-26 |
PH12015500717A1 (en) | 2015-05-18 |
BR112015007339A2 (en) | 2017-07-04 |
ZA201502709B (en) | 2017-07-26 |
CR20150220A (en) | 2015-09-16 |
IL238065B (en) | 2018-06-28 |
AU2013325149A1 (en) | 2015-04-16 |
EP2903433A4 (en) | 2016-04-20 |
NZ706334A (en) | 2018-09-28 |
AU2013325149B2 (en) | 2017-02-02 |
CL2015000847A1 (en) | 2016-03-28 |
JP2015530474A (en) | 2015-10-15 |
WO2014055208A2 (en) | 2014-04-10 |
SG11201502387QA (en) | 2015-04-29 |
RU2015116683A (en) | 2016-11-27 |
KR20150065792A (en) | 2015-06-15 |
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