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    公开号:ES2579946T9
    申请号:ES11703802.6T
    申请日:2011-02-09
    公开日:2016-10-20
    发明作者:Richard Jacobson；Yueqian Zhen
    申请人:AgroFresh Inc；
    IPC主号:
    专利说明:

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    DESCRIPTION
    Oil formulations comprising 1-methyl-cyclopropene Background
    This application claims the priority benefit in accordance with Title 35 of the United States Code article 119 (e) of Provisional Patent Application No. 61 / 309,073 filed on March 1, 2010.
    A convenient way for the storage and transport of cyclopropene compounds is in the form of complexes with molecular encapsulating agents. Said complex is useful, for example, for use in the treatment of plants or parts of plants by putting the plants or parts of plants in contact with the complex in order to produce contact between the plants or parts of plants and the cyclopropene . Such treatment of plants or parts of plants is often effective in the desirable disruption of one or more ethylene-mediated processes in plants or parts of plants. For example, such treatment of plant parts may sometimes desirably delay unwanted maturation. By way of another example, such treatment of crop plants before harvesting can sometimes improve crop yield.
    United States Patent Application Publication No. 2009/0035380 discloses an oil medium with particles dispersed in that oil medium and the particles contain cyclopropene compound and molecular encapsulating agent. The oil described by US 2009/0035380 is a liquid that is not water. In general, said oil easily allows the diffusion of the dispersed particles towards the limit between the oil and the air or water. When said particle finds said limit, the result is often the premature release of the cyclopropene compound from the particle.
    It is desirable to provide a composition in which the particles containing cyclopropene compound and the molecular encapsulating agent are dispersed in a continuous non-aqueous phase, where the composition does not allow such easy diffusion of the particles towards the limit of the non-aqueous continuous phase. It is contemplated that said composition would be useful for the treatment of plants or parts of plants, either by contacting the composition itself with the plants or parts of plants or by dispersing the composition in a diluent such as, for example, water, and then , putting the resulting dispersion in contact with the plants or parts of plants.
    Extract of the invention
    In one aspect of the present invention, a composition is provided that contains:
    (a) a non-aqueous pourable fluid comprising one or more alkylene carbonates;
    (b) drops dispersed in said pourable fluid (a), wherein said drops comprise:
    (i) a continuous non-aqueous phase that is a solid and
    (ii) solid particles dispersed in said continuous phase (i); wherein said solid particles (ii) have a size, measured by the largest dimension, of 100 micrometres or less; Y
    wherein said solid particles (ii) comprise 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin.
    In another aspect of the present invention, there is provided a method of treating plants or parts of plants that includes the step of contacting said composition with plants or parts of plants.
    Detailed description
    As used herein, a "fluid" is a material (which may be a single compound or a mixture of compounds) that is liquid at 25 ° C and at 1 pressure atmosphere and that has a boiling point at 1 atmosphere. pressure of 30 ° C or higher. As used herein, a fluid is "non-aqueous" if it contains, by weight, based on the weight of the fluid, 10% water or less. As used herein, a fluid is "pourable" if it has a viscosity at 25 ° C at a cut-off rate of 0.01 sec-1, 1 Pa * s (10 Poise) or less.
    The term "dispersed" herein means that individual masses of a material (the "dispersed" material, which can be presented in any divided form, such as liquid drops or solid particles) are distributed through a second material, which It forms a continuous medium around the particles. The system of individual masses dispersed in the continuous medium is known herein as a "dispersion." Each individual distributed mass of the dispersed material has multiple molecules of the dispersed material. Normally, the individual masses of the dispersed material have a median particle size of 10 nanometers or greater.
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    As defined herein, a "dispersant" is a compound that is capable of helping individual masses form a stable dispersion in a continuous medium. In the dispersion, part or all of the dispersant resides on the surface of the individual masses.
    As defined herein, it is said that a substance ("solute") is dissolved in another substance ("solvent") if the individual molecules of the solute are distributed through the solvent.
    As defined herein, it is said that a substance ("S1") is not soluble in a second substance ("S2") if, when preparing a mixture of 10 grams of S1 per 100 grams of S2, the The amount of S1 that dissolves in S2 is less than 1 gram of S1 per 100 grams of S2.
    As defined herein, an aqueous medium is a fluid that contains 50% or more of water by weight, based on the weight of that fluid.
    A compound is organic if it contains carbon and if it is not a compound normally considered inorganic, such as carbon oxides, carbides, carbon disulfide, metal cyanides, metal carbonyls, phosgene, carbonyl sulfide and others.
    In accordance with the present application, the "cloud temperature" is the temperature of a mixture above which all ingredients dissolve, usually to form a clear solution, and below which all or one or more of the ingredients disperse rather than dissolve in the solvent, to form a mixture with a cloudy appearance.
    Vinyl polymers are the result of the polymerization of the carbon-carbon double bonds of ethylenically unsaturated monomers. Vinyl polymers can be homopolymers (in which each repeating unit is the same), or they can be copolymers (containing two or more different repeating units).
    As used herein, an "acid group" is a group.
    chemical that contains at least one chain of carbon atoms that is at least 8 carbon atoms in length. A "fatty compound" is any compound that contains a fatty group.
    The practice of the present invention involves the use of one or more cyclopropene compounds with the formula:
    image 1
    where R1 is methyl and each of R2, R3 and R4 is hydrogen and the cyclopropene compound is known herein as "1-MCP".
    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 compounds, or a portion of one or more cyclopropene compounds. A complex that contains a cyclopropene compound molecule or a portion of a cyclopropene compound molecule encapsulated in a molecular encapsulating agent molecule is known herein as a "cyclopropene compound complex."
    In some embodiments, at least one cyclopropene compound complex is present which is an inclusion complex. In said inclusion complex, the molecular encapsulating agent forms a cavity, and the cyclopropene compound, or a portion of the cyclopropene compound is located within the cavity.
    Independently, in some of said inclusion complexes, the inside of the molecular encapsulating agent cavity is substantially apolar or hydrophobic, or both, and the cyclopropene compound (or the portion of the cyclopropene compound located within the 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 said apolar cyclopropene compound complexes, van der Waals forces or hydrophobic interactions, or both, make the cyclopropene compound molecule , or a portion thereof, remains within the cavity of the molecular encapsulating agent.
    The amount of molecular encapsulating agent can be usefully characterized by the relationship between the moles of molecular encapsulating agent and the moles of cyclopropene compound. In some embodiments, the ratio between the moles of molecular encapsulating agent and the moles of cyclopropene compound is 0.1 or higher; 0.2
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    0 higher; or 0.5 or higher; or 0.9 or higher. Independently, in some of said embodiments, the ratio between the moles of molecular encapsulating agent and the moles of cyclopropene compound is 10 or less; or 5 or less; or 2 or less or 1.5 or less.
    The encapsulating agent is alpha-cyclodextrin.
    In the practice of the present invention, a non-aqueous pourable fluid is used (herein, referred to as "fluid (a)") comprising one or more alkylene carbonates.
    In some embodiments, the fluid (a) contains one or more organic compounds. An organic compound contained in the fluid (a) is known herein as a "first" organic compound. Some suitable first organic compounds are liquid at 25 ° C and 1 atmosphere of pressure and have a boiling point at
    1 atmosphere of pressure, 30 ° C or higher.
    Some suitable first organic compounds have a viscosity, at 25 ° C and a cut-off index of 0.01 sec-1, of 1 Pa * sec (10 Poise) or less; 0.1 Pa * sec (1 Poise) or less; or 0.01 Pa * sec (0.1 Poise) or less. Mixtures of two or more first organic compounds are also contemplated, where the mixture has a viscosity, at 25 ° C and a cutting index of 0.01 sec-1, of 1 Pa * sec (10 Poise) or less; 0.1 Pa * sec (1 Poise) or less; or 0.01 Pa * sec (0.1 Poise) or less.
    Some suitable first organic compounds are polar compounds. Some suitable first organic compounds have a dipole moment (in Debye units) of 2.5 or higher; 3 or higher; or 3.5 or higher. Regardless, some suitable first organic compounds do not have hydrogen atoms attached to an electronegative atom. Some suitable first organic compounds have no hydrogen atom attached to an oxygen, nitrogen or sulfur atom. In some embodiments, a first organic compound is used in which each hydrogen atom is attached to a carbon atom.
    Some suitable first organic compounds include, for example, dialkyl ketones, alkylene carbonates, nitroalkanes and mixtures thereof. The first organic compound comprises at least one or more alkylene carbonates. In some embodiments, the first organic compound contains ethylene carbonate, propylene carbonate, butylene carbonate, or one of its mixtures. In some embodiments, the first organic compound contains propylene carbonate.
    In some embodiments, the amount of the first organic compound in the non-aqueous pourable fluid (a) is, by weight, based on the weight of the nonaqueous pourable fluid (a), 60% or more; or 75% or more; or 90% or more; or 95% or more. In some embodiments, the sum of the weights of all alkylene carbonates present in the non-aqueous fluid (a) is, by weight, based on the weight of the non-aqueous pourable fluid (a), 60% or more; or 75% or more; or 90% or more; or 95% or more. As used herein, "the weight of the non-aqueous pourable fluid (a)" means the weight of the fluid (a) itself, which includes the weight of any substance (if any) dissolved in the fluid (a ), and does not include the weight of any material (such as, for example, drops (b)) dispersed in the fluid (a).
    In the composition of the present invention, the drops (known herein as the "drops (b)") are dispersed in the fluid (a). Drops (b) contain a continuous phase (known herein as the "continuous phase (i)") that is solid. Drops (b) also contain solid particles (known herein as "solid particles (ii)") that are dispersed in the continuous phase (i). The continuous phase (i) is considered “continuous” because, within a single drop (b), the continuous phase (i) has the solid particles (ii) dispersed within it. It is contemplated that the mass of the continuous phase (i) located in a drop (b) will be isolated from other masses of the continuous phase (i) located in other drops (b), separated by the interposed fluid (a).
    The continuous phase (i) is solid. That is, it is a solid at 25 ° C.
    In some embodiments, the continuous phase (i) contains one or more organic compounds (known herein as "second organic compounds"). In some embodiments, one or more second organic compounds are used that are solid at 25 ° C, or otherwise, are liquids having a viscosity at 25 ° C, at a cut-off rate of 0.01 sec-1, of 25 Pa * s (250 Poise) or more. In some embodiments, one or more second organic compounds having a melting point of 50 ° C or higher are used. In some embodiments, one or more second organic compounds are used which are liquids having a viscosity at 25 ° C, at a cut-off rate of 0.01 sec-1, 25 Pa * s (250 Poise) or more; or 100 Pa * s (1000 Poise) or more; or 1000 Pa * s (10,000 Poise) or more; or 10,000 Pa * s (100,000 Poise) or more.
    Among the second suitable organic compounds that are solid at 25 ° C or that are high viscosity liquids at 25 ° C, there are many suitable compositions, including, for example, hydrocarbons, non-hydrocarbon waxes, fatty compounds, organic polymers and mixtures thereof . Suitable hydrocarbons include, for example, petroleum distillates, hydrocarbon waxes, petroleum jellies and mixtures thereof. Some suitable hydrocarbon waxes are, for example, polyethylene waxes, microcrystalline waxes, other synthetic waxes and mixtures thereof. Some suitable non-hydrocarbon waxes include, for example, waxes of biological origin, including,
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    for example, waxes containing compounds having the fatty acid esters structure of fatty alcohols. Some suitable waxes of biological origin include, for example, beeswax and carnauba wax.
    Suitable fatty compounds include, for example, fatty acids, esters of fatty acids, fatty acid amides and mixtures thereof. Suitable fatty compounds may be natural products (ie, products obtained from biological sources), modified natural products, synthetic compounds, or mixtures thereof. Suitable fatty compounds may be pure materials or may be mixtures of fatty compounds. Natural fatty compounds and modified natural fatty compounds are often mixtures. Some suitable modified natural fatty compounds include, for example, natural fatty compounds that have been hydrogenated, hydroxylated, sulphonated, polymerized or one of their combinations.
    A suitable fatty compound is stearic acid, which can be used in pure form or in the form of a mixture, which can be obtained from a biological source.
    A group of suitable fatty compounds are glycerides. Glycerides are monosteres, diesters and glycerol triesters. Suitable glycerides are fatty glycerides, which are compounds in which at least one acid group is attached to the glycerol molecule with an ester bond. Some suitable glycerides are vegetable oils (i.e., plant-produced oils) or modified vegetable oils or one of their mixtures. Some suitable glycerides are, for example, hydrogenated plant oils. Suitable glycerides include, for example, hydrogenated soybean oil and hydrogenated cottonseed oil.
    Some compounds that are suitable as the second organic compound are compounds with a relatively low dipole moment. In some embodiments, one or more second organic compounds are used that have a dipole moment of 1.5 Debye or less; or 1.0 Debit or less; or 0.8 Debye or lower. In some embodiments, each second organic compound has a dipole moment of 1.5 Debye or less; or 1.0 Debit or less; or 0.8 Debye or lower.
    In some embodiments, the amount of all second organic compounds in the continuous phase (i) is, by weight, relative to the weight of the continuous phase (i), 60% or more; or 75% or more; u 85% or more; or 95% or more; or 99% or more. As used herein, "the weight of the continuous phase (i)" means the weight of the continuous phase (i) by itself, which includes the weight of any substance (if any) dissolved in the continuous phase. (i) and that does not include the weight of any material (such as, for example, solid particles (ii)) dispersed in the continuous phase (i).
    Among the embodiments in which one or more first organic compounds are present, and in which one or more second organic compounds are present, the mixture of all the second organic compounds that are present is not soluble (as defined hereinbefore. memory) in the mixture of all the first organic compounds that are present. In some embodiments, the mixture of all second organic compounds is not soluble in the mixture of all first organic compounds at 25 ° C. In some embodiments, the mixture of all second organic compounds is not soluble in the mixture of all first organic compounds over a temperature range from 20 ° C to a maximum temperature, where that maximum temperature is 40 ° C or higher; or 50 ° C or higher; or 75 ° C higher.
    In some embodiments (referred to herein as "polymer mixture" or "PM"), the continuous phase (i) contains a mixture (referred to herein as "PM mixture") of an organic polymer and an organic fluid (referred to herein as "PM fluid"). In some embodiments of PM, that PM mixture is a dispersion of the polymer in the PM fluid. In some embodiments of PM, that PM mixture is a solid (such as, for example, a gel) at 25 ° C. In some embodiments of PM, the PM mixture, at a certain temperature of 50 ° C or higher, is a liquid having a viscosity at 0.01 sec-1, less than 25 Pa * s and the PM mixture, at 25 ° C , is a solid.
    In some embodiments of PM (referred to herein as "viscosity decrease" embodiments), the PM mixture has a low viscosity temperature range. That is, there is a temperature range over which the viscosity of the PM mixture at 0.01 sec'1 is 10 Pa * s or less. In embodiments of viscosity decrease, the lower end of the low viscosity temperature range is 30 ° C or higher or 50 ° C or higher. In embodiments of viscosity reduction, the upper end of the low viscosity temperature range is 180 ° C or less, or 150 ° C or less, or 100 ° C or less. In embodiments of viscosity reduction, the PM mixture is a solid or is a liquid in a temperature range that includes the range of 18 ° C to 28 ° C. It is contemplated that the PM mixture can be heated in the low viscosity range for ease of agitation and / or mixing and then cooled or allowed to cool to 25 ° C, to become a solid.
    In some embodiments of viscosity decrease (referred to herein as "cloud temperature" embodiments), the PM mixture has a cloud temperature that is greater than 30 ° C and less than 100 ° C. In some embodiments of cloud temperature, it is possible to heat the PM mixture above the cloud temperature, for agitation and / or convenient mixing (because the PM mixture has a viscosity, at 0.01 sec-1, of less than 10 Pa * s, at a certain temperature above the cloud temperature), and then cool the PM mixture below the cloud temperature, whereby the mixture
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    PM becomes a solid.
    In some embodiments of PM, the PM fluid contains, for example, one or more hydrocarbon materials. A suitable hydrocarbon material may be a single hydrocarbon substance or it may be a mixture of hydrocarbon substances. Some suitable hydrocarbon materials are, when tested in the absence of any dissolved or dispersed solid compound, liquids with viscosity at 25 ° C and a cut-off rate of 0.01 sec'1, 1 Pa * sec (10 Poise) or less . Some suitable hydrocarbon materials are, for example, petroleum hydrocarbons.
    Some embodiments of PM contain, for example, one or more vinyl polymers. Suitable vinyl polymers include, for example, polymers and copolymers made from one or more monomers such as, for example, styrene, substituted starches, (meth) acrylic acid, esters of (meth) acrylic acid, substituted acid esters (meth) acrylic, amides of (meth) acrylic acid, substituted amides of (meth) acrylic acid, alkenes, vinyl asters of carboxylic acids, halosubstituted alkenes and mixtures thereof. Suitable alkenes include, for example, ethylene, propylene, dienes and mixtures thereof. Suitable vinyl esters of carboxylic acids include, for example, vinyl acetate. In some embodiments, one or more copolymers of ethylene and vinyl acetate are used.
    In some embodiments of PM, a solvent having a dipole moment of 1.5 Debye or less is used; or 1.0 Debit or less; u 8 Debye or less.
    In some embodiments of PM, the amount of PM mixture in the continuous phase (i) is, by weight, based on the weight of the continuous phase (i) (as defined hereinbefore), 60% or more; or 75% or more; u 85% or more; or 95% or more or 99% or more.
    Among the embodiments of PM, the PM fluid is not soluble (as defined hereinbefore) in the mixture of all the first organic compounds present. In some embodiments, the PM fluid is not soluble in the mixture of all the first organic compounds at 25 ° C. In some embodiments, the PM fluid is not soluble in the mixture of all the first organic compounds in a temperature range from 20 ° C to a maximum temperature, where that maximum temperature is 40 ° C or higher; 50 ° C or higher; or 75 ° C or higher.
    Also contemplated are the embodiments in which the continuous phase (i) contains a mixture of two or more of the second organic compounds described hereinbefore.
    The continuous phase (i) is not soluble in the pouring fluid (a). In some embodiments, the continuous phase (i) is not soluble in the pourable fluid (a) at 25 ° C. In some embodiments, the continuous phase (i) is not soluble in the pourable fluid (a) in a temperature range from 20 ° C to a maximum temperature, where that maximum temperature is 40 ° C or higher; 50 ° C or higher; or 75 ° C or higher.
    In the composition of the present invention, the drops (b) also contain solid particles (ii) that are dispersed in a continuous medium (i).
    In the particles of the present invention that are dispersed in the continuous medium (i) the median size, measured by the largest dimension, is 100 micrometers or less. That is, the set of particles is evaluated to determine the size. A suitable method of evaluation, for example, is inspection using a microscope. The images of the particles, for example, those images obtained in a microscope, can be inspected and evaluated visually, possibly with reference to the standards of length; or alternatively, the images may be inspected and evaluated by means of appropriate image analysis methods, for example, by computer programs.
    In the embodiments in which the particles are not spherical, it is useful to characterize the particles by the largest dimension of each particle. A set of particles can be characterized by the median value of the largest dimension. That is, half of the particles in the set, by weight, will have the largest dimension, which is larger than the median of the set. In the practice of the present invention, when evaluating the set of particles dispersed in the continuous phase (i), that median value is 100 micrometres or less. In some embodiments, particles are used in which the median value is 50 micrometres or less; 20 micrometres or less; or 10 micrometres or less; or 5 micrometres or less; or 2 micrometres or less.
    In some embodiments, the solid material is manufactured as a powder but the particle size of that powder is greater than desirable for use as solid particles (ii). In such embodiments, the powder may be subjected to a process that reduces particle size. One of such suitable processes is air grinding.
    An independent measure of a particle is the aspect ratio, which is the relationship between the largest particle size and the smallest particle size. The aspect ratio is independent of the particle size. In some embodiments of the present invention, the set of dispersed particles (ii), dispersed in the continuous phase (i), has an aspect ratio of 20 or less; or 10 or less; or 5 or less; or 2 or less.
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    The dispersed particles (ii) contain cyclopropene compound and molecular encapsulating agent. In some embodiments, part or all of the cyclopropene compound present in the composition is part of a cyclopropene compound complex. While the present invention is not limited to any particular theory or model, it is contemplated that most or all of the cyclopropene compound molecules present in the composition are present in the form of molecules that are part of cyclopropene compound complexes. It is further contemplated that any molecule of cyclopropene compound in the composition, which is not part of a complex of cyclopropene compound, is present, for example, in solution, adsorbed by an interface, in some other location, or in one of its combinations In some embodiments, the amount of cyclopropene compound present as part of a cyclopropene compound complex, by weight, based on the total amount of cyclopropene compound in the composition, is 80% or more; or 90% or more, or 95% or more or 99% or more.
    In some embodiments, the dispersed particles (ii) contain only one or more cyclopropene compounds and one or more molecular encapsulating agents. In some embodiments, the dispersed particles (ii) contain one or more additional compounds. When additional compounds are present, they can be incorporated into the same solid particle as the molecular encapsulating agent and cyclopropene, or they can be incorporated into separate solid particles, or one of their combinations.
    Some suitable additional compounds that can be included in the dispersed particles (ii) are, for example, inert solid powders (i.e., powders that do not participate in the molecular encapsulation process and that do not chemically react with the other ingredients of the dispersed particles ( ii)). Some suitable inert solid powders include, for example, carbohydrates such as dextrose. When inert solid powders are used, they may be present in an amount, by weight, based on the weight of the dispersed particles (ii), which is more than 0% and is 99% or less. In some embodiments, the amount of inert solid powders is 5% to 20%.
    Other suitable additional compounds that may be included in the dispersed particles (ii) are, for example, one or more amino acid salts, which, if present, may be present in an amount, by weight, based on the weight of the dispersed particles ( ii), which is more than 0% and which is 5% or less. In some embodiments, the amount of amino acid salts is from 1% to 3%.
    Other suitable additional compounds that may be included in the dispersed particles (ii) are, for example, water, which, if present, may be in an amount, by weight, based on the weight of the dispersed particles (ii), which is more of 0% and that is 20% or less. In some embodiments, the amount of water is from 1% to 9%.
    In some embodiments of the present invention, the continuous phase (i) contains one or more dispersants (referred to herein as "p dispersant"). It is contemplated that part or all of the dispersant p dissolves in the continuous phase (i), that part or all of the dispersant p is located at the interfaces between the dispersed particles (ii) and the continuous phase (i) (i.e. , on the surface of the dispersed particles (ii)), or one of their combinations. Likewise, it is contemplated that a certain amount of the dispersant p (or none) can be located in one or more places, for example, on the surface of the continuous phase (i), on the walls of the container, in a complex with a molecular encapsulating agent , in another place in the composition, or one of its combinations.
    Some dispersants p suitable for use in the continuous phase (i) are vinyl polymers. Some suitable dispersants are vinyl polymers that are homopolymers or that are statistical copolymers of two or more monomers. A suitable dispersant contains one or more polymers that have repetitive units of the following structure:
    R5
    /
    H, C — HC
    image2
    where each of R5, R6, R7 and R8 is an alkyl group and n is 10 or higher. Such polymers are known as alkylated polyvinylpyrrolidone. A suitable alkylated polyvinylpyrrolidone is AGRIMER ™ AL-22 dispersant, from ISP Corp.
    Other dispersants p suitable for use in the continuous phase (i) are poly (ethylene oxide) polymers bonded to a hydrophobic group. Suitable hydrophobic groups include, for example, poly (propylene oxide), poly (oxide of
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    butylene) and polyhydroxystearic acid. Some suitable p dispersants include, for example, Atlox ™ 4912 dispersant and Atlox ™ 4914 dispersant, from Croda Corp.
    In some embodiments, the pourable fluid (a) contains one or more dispersants (referred to herein as "dispersants d"). It is contemplated that part or all of the dispersant d is dissolved in the pourable fluid (a), that part or all of the dispersant d is located at the interfaces between the drops (b) and the pourable fluid (a) (i.e., on the surfaces of the dispersed drops (b)), or one of their combinations. Additionally, it is contemplated that a certain amount of the dispersant d (or none) can be located at one or more sites, such as, for example, on the surface of the pouring fluid (a), on the walls of the container, at another site in the composition , or one of its combinations.
    One or more dispersants d, if present, may have the same composition as one or more dispersants p. In some embodiments, one or more dispersants d are present which have a different composition from any of the dispersants p of the present invention. In some embodiments, one or more dispersants p are presented which have a different composition of the dispersants d of the present invention. In some embodiments, each dispersant p is different from each dispersant d.
    Some suitable dispersants are vinyl polymers. Some suitable d dispersants are vinyl polymers that are homopolymers or that are statistical copolymers of two or more monomers. In some embodiments, one or more dispersants d which are copolymers of vinyl pyrrolidone with vinyl acetate are used.
    In some embodiments, one or more particulate minerals are presented in the composition. In some embodiments, smoke smoke is present. The smoke shaft usually has an average particle size of 5 to 50 nm. In some embodiments, the smoke silica that is present has been treated with dimethyldichlorosilane. The smoke silica, if present in the composition, can be present in one or both of the pourable fluid (a) and the continuous phase (i).
    In some embodiments, the amount of dispersant p, by weight, based on the total weight of the dispersed drops (b), is 0.2% or more; or 0.5% or more; or 1% or more. Regardless, in some embodiments, the amount of dispersant p, by weight, based on the total weight of the dispersed drops (b), is 5% or less or 10% or less.
    In some embodiments, the amount of solid particles (ii), by weight, based on the total weight of the dispersed drops (b), is 10% or more; or 20% or more; or 50% or more. Regardless, in some embodiments, the amount of solid particles (ii), by weight, based on the total weight of the dispersed drops (b), is 80% or less; or 70% or less.
    In some embodiments, the amount of drops (b), by weight, based on the total weight of the composition, is 5% or more; or 10% or more; or 20% or more. Regardless, in some embodiments, the amount of drops (b), by weight, based on the total weight of the composition, is 70% or less; or 60% or less; or 50% or less; or 40% or less.
    In some embodiments, the amount of particulate mineral present is based, by weight, based on the total weight of the composition, is 0.2% or more; or 0.5% or more; or 1% or more; or 2% or more. Regardless, in some embodiments, the amount of particulate mineral present, by weight, based on the total weight of the composition, is 20% or less; or 10% or less; or 5% or less. In some embodiments, no particulate mineral is present.
    In some embodiments, the amount of dispersant d present, by weight, based on the total weight of the composition, is 0.1% or more; or 0.2% or more; or 0.5% or more; or 1% or more. In some embodiments, the amount of dispersant d present, by weight, based on the total weight of the composition, is 10% or less; or 5% or less; or 2% or less.
    Some methods suitable for the use of the composition of the present invention involve placing the entire composition in water or in an aqueous medium. In some embodiments, the composition is placed in an aqueous medium containing water in an amount, by weight, based on the weight of the aqueous medium, of 75% or more; or 90% or more; or 95% or more. In some of said embodiments, the amount of the composition, by weight, based on the sum of the weights of the composition and the water or the aqueous medium, is 0.1% or more, or 0.2% or more; or 0.5% or more; or 1% or more; or 2% or more; or 5% or more; or 10% or more; or 20% or more. In some of said embodiments, the amount of the composition, by weight, based on the sum of the weights of the composition and the water or the aqueous medium, is 80% or less; or 60% or less.
    When it is intended to place the composition of the present invention in water, it is sometimes convenient to include an emulsifier in the composition of the present invention, before mixing the composition of the present invention with water. Some suitable emulsifiers include, for example, cationic surfactants, anionic surfactants, amphoteric surfactants, non-ionic surfactants and their compatible mixtures.
    Some suitable anionic surfactants include, for example, those with anions selected from sulfates, sulphonates, carboxylates and mixtures thereof. Some suitable cationic surfactants include, for example, those with quaternary ammonium cations. Some suitable amphoteric surfactants include, for example, betalnas.
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    Some suitable non-ionic surfactants, for example, are block copolymers. Some suitable block copolymers are, for example, block copolymers based on butyl. When an emulsifier is present in the composition of the present invention, the amount may be, for example, by weight, based on the total weight of the composition, 0.5% or more; or 1% or more; or 5% or more. Independently, in some embodiments, the amount of emulsifier may be, for example, by weight, based on the total weight of the composition, 15% or less; or 10% or less; or 7% or less.
    When the composition of the present invention is placed in water or in an aqueous medium, it is sometimes desirable that part or all of the composition be dispersed in the water or aqueous medium. In some embodiments, part or all of the pourable fluid (a) can be dissolved in the water or aqueous medium and the droplets (b) can be dispersed in the water or aqueous medium. In some embodiments, part or all of the pourable fluid (a) will be dispersed in the water or aqueous medium, either in discrete masses separated from the droplets (b), or in discrete masses containing each part of the pourable liquid (a ) and one or more droplets (b).
    When the composition of the present invention is placed in an aqueous medium, in some embodiments the amount of cyclopropene compound, by weight, based on the total weight of the composition, plus the aqueous medium, is 1 part per million (ppm) or higher; or 10 ppm or higher. Regardless, in some embodiments, the amount of cyclopropene compound, by weight, based on the total weight of the composition, plus the aqueous medium, is 1,000 ppm or less or 500 ppm or less.
    When a cyclopropene compound complex is used, direct contact between the cyclopropene compound complex and water sometimes causes the release of the cyclopropene compound from the complex earlier than desired and the cyclopropene compound may be lost (for example, by diffusion of the composition, by chemical reaction or a combination of these). It is contemplated that, in the practice of these embodiments of the present invention in which the composition of the present invention is mixed with water, the cyclopropene compound complex remains in the solid particles (ii), so that the contact between the complex of cyclopropene compound and water is minimized or eliminated and, therefore, a desirably high fraction of the molecules of the cyclopropene compound of the composition remains in the composition for a time that is not undesirably short.
    In some embodiments, the composition of the present invention is liquid in a temperature range of 15 ° C or less than 30 ° C or higher.
    A possible use of the composition of the present invention is for the treatment of plants or parts of plants by putting a composition of the present invention in contact with the plants or parts of plants. Such contact can be made in different ways. For example, a composition of the present invention can be contacted directly with plants or parts of plants. In another example, a composition of the present invention can be mixed with a diluent and the resulting mixture can be brought directly into contact with plants or parts of plants. In some embodiments, such a diluent may be water or an aqueous medium (as described hereinbefore).
    A liquid composition (which may be a composition of the present invention or a mixture of a composition of the present invention with a diluent) may be properly contacted with plants or plant parts by any method, including, for example, spraying, immersion, soaking, fogging and combinations thereof. Some suitable methods include spraying or immersion or a combination thereof. In some embodiments spraying is used. When spraying is used, it is contemplated that a liquid composition of the present invention is sprayed on all or part of the surfaces of plants or parts of plants. When immersion is used, it is contemplated that parts of the plant are immersed in a liquid composition of the present invention.
    Plants that produce parts of useful plants are referred to herein as "crop plants." The treatment can be carried out on growing plants, or on parts of plants that have been harvested from growing plants. It is contemplated that, when performing the treatment on growing plants, the composition of the present invention may contact the entire plant, or may contact one or more parts of plants. Parts of plants include any part of a plant, for example, flowers, buds, florescence, seeds, cuttings, roots, bulbs, fruits, vegetables, leaves, and combinations thereof.
    The collection of useful plant parts of crop plants is known as harvest. In some embodiments, the crop plants are treated with a composition of the present invention before harvesting the useful plant parts.
    Appropriate treatments can be performed on plants that are planted in a field, in a garden, in a building (for example, a greenhouse), or elsewhere. Appropriate treatments can be carried out on plants planted in the open soil, in one or more containers (for example, a pot, a planter or a vase), in restricted or raised beds, or in other places. In some embodiments, the treatment is performed on plants that are located in a different place in a building. In some embodiments, the plants are treated while growing in containers such as pots, seedbed drawers or portable beds.
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    Many of the plants that are suitable for use in the practice of the present invention can be usefully divided into categories or groups. A useful method for the definition of such groups is that described in: "Definition and Classification of Commodities", published on March 23, 2006, or previously, by the United Nations Organization for Food and Agriculture (FAO ), as a “draft”.
    In the practice of some embodiments of the present invention, the use of plants that produce one is contemplated
    0 more crops found within any of the following crop groups.
    The crop group 1 comprises cereals, which include, for example, wheat, rice, barley, corn, palomerous corn, rye, oats, millet, sorghum, buckwheat, quinoa, millet millet, triticale, alpiste, canagua, amaranth, adlai , wild rice and other cereals. The crop group 3 comprises sugar crops, which include, for example, sugar cane, sugar beet, sugar syrup, sugar sorghum, sugar palm and other sugar crops. The crop group 4 comprises legumes, which include, for example, beans, chickpeas, peas, black-eyed beans, guandul, lentils and other legumes. The crop group 5 includes nuts, which include, for example, Brazil nut, cashew nuts, chestnuts, almonds, walnuts, pistachios, hazelnuts, pecan nuts, macadamia nuts and other nuts. The crop group 6 comprises oil crops, which include, for example, soybeans, peanuts, coconut, oil palm fruit, olives, Karite nuts, castor nuts, sunflower seeds, rapeseed seed, canola, Tung nuts, Cacao seed, sesame seed, mustard seed, poppy seed, melon seed, tallow tree seeds, Kapok fruit, cottonseed seed, flaxseed seed, hemp seed and other oilseeds. In some embodiments, soy plants are suitable. The crop group 7 includes vegetables, which include, for example, cabbages, artichokes, asparagus, lettuce, spinach, cassava leaves, tomatoes, cauliflower, squash, cucumbers and gherkins, eggplants, chili and peppers, green onions, dried onions, garlic, leek, other alliaceous vegetables, green beans, green peas, beans, green beans, carrots, ocra, green corn, mushrooms, watermelons, melons, bamboo shoots, beets, chard, capers, thistles, celery, chervil, watercress, Fennel, horseradish, oregano, goat's beard, parsley, chirivia, radish, rhubarb, rutabaga, savory, plants of the genus Scorzonera, sorrel, watercress and other vegetables. The crop group 8 comprises fruits, which include, for example, bananas and bananas, citrus fruits; pips fruits; bone fruits; berries; grapes; tropical fruits; various fruits; and other fruits. The crop group 9 comprises fibers, which include, for example, cotton, linen, hemp, kapok, jute, ramie, sisal and other plant fibers. In some embodiments, cotton plants are suitable. The crop group 10 comprises spices. Crop group 11 comprises forage crops. Forage crops are crops that are grown primarily for animal feed. The crop group 12 comprises stimulating cultures, which include, for example, coffee, cocoa, tea, mate, other plants used for the preparation of infusions such as teas, and other stimulating cultures. The crop group 13 comprises tobacco and rubber and other crops, which include, for example, plant oils used in perfume, food and other industries, pyrethrum, tobacco, natural rubber, natural gums, other resins and vegetable waxes.
    In some embodiments, the present invention involves the treatment of any non-citric plant (ie, any plant that is not of the Citrus genus). In other embodiments, the practice of the present invention is limited to the treatment of non-citrus plants. Regardless, in some embodiments, all plants that are treated are not members of the Nicotian genus.
    In some embodiments, the composition of the present invention is used for the treatment of crop plants growing in a field. Said treatment operation can be carried out once or more than once in a particular group of crop plants, during a single growing season. In some embodiments, the amount of cyclopropene compound used in a treatment is 0.1 grams 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. Regardless, in some embodiments, the amount of cyclopropene compound used in a spraying operation is 6000 g / ha or less; or 3000 g / ha or less; or 1500 g / ha or less.
    The embodiments in which the parts of harvested plants are treated are also contemplated.
    In some embodiments that involve adding the composition of the present invention to water or an aqueous medium, the water or aqueous medium contains one or more chelating agents. A chelating agent is a compound that contains two or more electron donor atoms capable of forming two or more coordinated bonds with a metal atom.
    In embodiments in which one or more chelating agents are used, suitable chelating agents include, for example, organic and inorganic chelating agents. In some embodiments, the chelating agent includes one or more aminocarboxylic acids, one or more of its salts, one or more hydroxycarboxylic acids, one or more of its salts, one or more oximes or one of its mixtures. Some suitable aminocarboxylic acids include, for example, the neutral or saline forms of ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), N-dihydroxyethylglycine (2-HxG) and ethylenegyl (hydroxyglyph) (hydroxyglycyl) (ethylene glycol) their mixtures Some suitable hydroxycarboxylic acids include, for example, the neutral or salt forms of tartaric acid, citric acid, gluconic acid, 5-sulfosalicylic acid and mixtures thereof. Some suitable oximes include, for example, dimethylglioxime, salicylalloxime and mixtures thereof. In some embodiments, the neutral or saline form of EDTA is used. In some embodiments, metal complexing agent is not used.
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    It is understood that, for the purposes of the present specification and claims, unless specifically stated otherwise, operations are performed at 25 ° C and at 1 atmosphere of pressure in the air.
    Examples
    In the Examples that follow, the following materials were used.
    Complex 1 = Dry powder containing 1-MCP and alpha-cyclodextrin complex, with 4.7% of 1-MCP by weight. Complex 1 was ground with air so that the median size, measured by the largest dimension, was less than 50 micrometers.
    HC01 = ISOPAR ™ V hydrocarbon, C12 to C20 petroleum hydrocarbons, from ExxonMobil Chemical.
    PAVP = AGRIMER ™ AL-22 dispersant, alkylated vinyl pyrrolidone polymer, ISP Corporation.
    PVPVA = AGRIMER ™ VA51 dispersant, copolymer of vinyl pyrrolidone and vinyl acetate, ISP Corporation.
    BCP = TOXIMUL ™ 8320 emulsifier, block copolymer based on butyl, Stepan Co.
    Sllice 1 = AEROSIL ™ R972 sllice, smoke sllice, treated with dimethyldichlorosilane, particle size 5 to 50 nanometers, Evonik Industries.
    PC = JEFFSOL ™ AG-1550 solvent, contains propylene carbonate, Huntsman Performance Products.
    Wax = paraffin wax, melting point: 53-57 ° C, Aldrich Chemical.
    Soy = DRITEX ™ S hydrogenated, fully hydrogenated soybean oil, Stratus Foods.
    EVA = ELVAX ™ 250 ethylene-vinyl acetate copolymer, DuPont.
    HC02 = UNIPAR ™ 260 petroleum hydrocarbons, UniSource Energy, Inc.
    "Base" (for pourable fluid (a))
    2.50 g of Sllice 1 and 55.51 g of PC were mixed and dispersed with a high cut mixer in order to form a suspension, which was heated from 60 ° C to 70 ° C.
    Comparative Example A
    Droplet formulation. 13.44 g of HC01 and 0.65 g of PAVP were mixed and heated from 60 ° C to 70 ° C, and then mixed with 21.50 g of Complex 1. While still at 60 ° C at 70 ° C This drop formulation was combined with a base (also from 60 to 70 ° C) and dispersed with a high cut mixer until the viscosity had a very thick appearance. 1.4 g of PVPVA was added, and the mixture was stirred by hand. Then, 5.00 g of BCP was added, and the mixture was stirred by hand. After the addition of PVPVA and BCP, the viscosity seemed to decrease somewhat. The resulting emulsion was allowed to cool to 25 ° C. This is a Comparative Example, since HC01 is not a high viscosity liquid at 25 ° C.
    Examples 1, 3 and 4
    Compositions were prepared using the method of Comparative Example A, except that 13.44 g of HC01 were replaced with 13.44 g of a different ingredient, as follows.
    Example 1 used wax (solid at 25 ° C).
    Example 2 used soy (solid at 25 ° C).
    Example 3 used a solution of EVA in HC02 (EVA 10% by weight based on the weight of the solution) (gel at 25 ° C).
    Observations:
    Each example was diluted in propylene carbonate, and the result was observed with an optical microscope with an increase of 400 X. In addition, each example was diluted in water, and the result was observed with an optical microscope with an increase of 400 X. In each case, it was observed that the particles of Complex 1 dispersed within the drops and it was observed that the drops dispersed throughout the entire field of vision.
    It was observed that the particles of Complex 1 were dispersed within the drops, whose composition was that of the Drop Formulation, in each example.
    Observations of the diluted formulations showed that each of Examples 1, 3 and 4 had Complex 1 particles that acted as solid particles (ii). These particles were dispersed within the prepared drops of the various Drop Formulations, which acted as the drops (b). The drops were dispersed within the propylene carbonate, which acted as the pouring fluid (a).
    权利要求:
    Claims (9)
    [1]
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    1. A composition comprising:
    (a) a non-aqueous pourable fluid comprising one or more alkylene carbonates;
    (b) drops dispersed in said pourable fluid (a), wherein said drops comprise:
    (i) a continuous non-aqueous phase that is a solid and
    (ii) solid particles dispersed in said continuous phase (i);
    wherein said solid particles (ii) have an average size, measured by the largest dimension, of 100 micrometers or less; Y
    wherein said solid particles (ii) comprise 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin.
    [2]
    2. The composition of claim 1, wherein said pourable fluid (a) comprises one or more organic compounds with a dipole moment of 2.5 debits or greater.
    [3]
    3. The composition of claim 1, wherein said continuous phase (i) comprises one or more organic compounds with a dipole moment of 1.5 debits or less.
    [4]
    4. The composition of claim 1, wherein the dispersed particles (ii), dispersed in the continuous phase (i), have an aspect ratio of 20 or less.
    [5]
    5. The composition of claim 1, wherein the ratio between moles of alpha-cyclodextrin and moles of 1- methylcyclopropane (1-MCP) is in the range of 0.1 to 10.
    [6]
    6. A composition obtained by placing the composition of claim 1 in water or in an aqueous medium.
    [7]
    7. The composition of claim 6, wherein the amount of water is 50% or more, by weight, based on the weight of said composition.
    [8]
    8. A method of treating plants or parts of plants, comprising the step of contacting said plants or parts of plants with the composition of claim 1.
    [9]
    9. The method of claim 8, wherein said method comprises the step of contacting said plants or parts of plants with the composition of claim 7.
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    PCT/US2011/024120|WO2011109144A1|2010-03-01|2011-02-09|Oil formulations comprising cylcopropene compounds|
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