CN104884517A - Compositions with hot melt resin matrix - Google Patents
Compositions with hot melt resin matrix Download PDFInfo
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- CN104884517A CN104884517A CN201280077126.8A CN201280077126A CN104884517A CN 104884517 A CN104884517 A CN 104884517A CN 201280077126 A CN201280077126 A CN 201280077126A CN 104884517 A CN104884517 A CN 104884517A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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Abstract
The invention provides compositions, which comprises a collection of coated particles, wherein the coated particles comprises an active ingredient dispersed in an resin matrix; and a coating comprising at least one hydrophobic compound. Also provided are methods for preparing compositions comprising: (a) blending an active ingredient (for example, 1-MCP complex powder) with resin at the temperature slightly over the melting point of the resin; (b) dispersing the blend into an oil medium containing hydrophobic particles by shearing and obtain an oil dispersion; and (c) consolidating the resin particles by cooling. Thus, the active ingredient (for example, 1 -MCP complex powder) is imbedded in the resin matrix spheres, and the hydrophobic particles, which also serve as Pickering emulsifier to stabilize the matrix spheres, form a coating layer around the matrix spheres to provide protection against water. Thus, the sphere is composed of the "Pickering" particle and resin matrix, in which the active ingredient is imbedded.
Description
Background technology
Ethene is the growth of plant, grows, old and feeble, and the important conditioning agent of environmental stress, major effect plant maturation, the correlated process that flower is decayed and leaf falls.Ethene is growth period or produce in a large number in the storage and transport process of plant under plant is in environmental stress normally.Therefore, plant as fruit and cereal can before results heat or arid in reduce output.As results after vegetables, the commercial value of the fresh plant such as fruit and flower can accelerate the maturation of fruit due to too much ethylene gas, flower decay and leaf early fallout and reduce.
In order to prevent the disadvantageous effect of ethene, use 1-methylcyclopropene (1-MCP) occupy ethylene receptor, therefore ethene can not in conjunction with and work.1-MCP to the avidity of acceptor than ethene to the avidity of acceptor approximately large 10 times.1-MCP also affects the biosynthesizing of some species by feedback inhibition.Therefore, 1-MCP be widely used in gather in the crops after fresh-keeping and results before plant protection.
But 1-MCP is difficult to operation, because it is one have high chemically active gas.In order to overcome this problem, by 1-MCP gas dissolving is formed water-in-oil emulsion in inner oil phase, 1-MCP gas is successfully encapsulated, but in the final product, the concentration of 1-MCP still very low (<50ppm).
Therefore, in current agricultural application, 1-MCP and cyclodextrin to form powder, and can discharge 1-MCP gas when powder dissolution is in water.The ease of use of this powder-product is the product considerably beyond gas form, but they still have shortcoming, comprising: when (1) is in field or at this powder of enclosed space process, be not user-friendly; (2) this powder type can not stably and equably suspend in water, this nonuniform delivery that will 1-MCP caused plant, and the uneven slaking reaction of plant; (3) after contacting with water, 1-MCP discharges in a short period of time completely, and this is far early than the expected time, and therefore some or all of 1-MCP is lost in surrounding environment.Therefore, apply in the on-the-spot water for delay plant maturation for being adapted at, 1-MCP powder-product is not correct formula.
In addition, in order to the effort solved the problem comprises the material mixing of powder by 1-MCP mixture and other powder type, then prepare effervescent tablet and maybe this mixture is encapsulated in fluid-tight container.But such improved composition still has shortcoming, comprise: (1) is similar to the limitation of powder, they remain conditional in the application, because they need air circulation to guarantee being uniformly distributed of 1-MCP usually, this is unavailable in applying at the scene; (2) they can not on-the-spotly be used by spraying.Therefore, still need a kind of composition not having these shortcomings, it comprises the compound of cyclopropylene or other plant-growth regulator for sending.
Summary of the invention
The invention provides the composition containing coating particles set, wherein this coating particles comprises the activeconstituents be dispersed in resinous substrates; With the coating comprising at least one hydrophobic compound.Additionally provide the method for the preparation of composition, comprising: activeconstituents (such as, the powder of 1-MCP mixture) mixes with resin by (a) at just over the temperature of this melting point resin; B () by shearing the oily medium be distributed to by this mixture containing hydrophobic particles, and obtains oil dispersion liquid; (c) by this resin particle of cooling curing.Therefore, described activeconstituents (such as, 1-MCP composite powder) is embedded in resinous substrates ball, and described hydrophobic particle, it also serves as pik woods (Pickering) emulsifying agent to stablize this matrix ball, forms coating around this matrix ball with waterproof.Therefore, this ball is made up of " pik woods " particle and resinous substrates, embeds activeconstituents wherein.
In one aspect, provide a kind of composition comprising the set of coating particles, wherein, each described coating particles comprises,
A () is dispersed in the activeconstituents in resinous substrates; With
B () comprises the coating of at least one hydrophobic compound.
In the embodiment of a composition provided, described activeconstituents comprises volatile compound.In further embodiment, described volatile compound comprises cyclopropylene.In further embodiment, described cyclopropylene comprises 1-methylcyclopropene (1-MCP).In another embodiment, described activeconstituents comprises the mixture containing cyclopropylene and molecular encapsulation agent.In further embodiment, described molecular encapsulation agent comprises alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin, or their combination.
In one embodiment, described activeconstituents comprises plant-growth regulator.In another embodiment, described resinous substrates comprises vibrin.In another embodiment, described resinous substrates comprises polyester, polyethers, epoxy resin, isocyanic ester, ethylene vinyl acetate copolymer, natural or synthesis wax or their combination.In another embodiment, described resinous substrates comprises polycaprolactone polyol.
In one embodiment, the molecular weight that described polycaprolactone polyol has is 1,000 to 200,000; From 2000 to 50000; From 2000 to 8000; Or from 2000 to 4000.In another embodiment, the fusing point of described polycaprolactone polyol is from 30 degrees Celsius to 120 degrees Celsius; From 40 degrees Celsius to 80 degrees Celsius; Or from 50 degrees Celsius to 60 degrees Celsius.In another embodiment, described at least one hydrophobic compound comprises hydrophobic silica.In further embodiment, by the silica sphere of silane coupling agent or this hydrophobic silica of organosilicon modifier modification.In another embodiment, described at least one hydrophobic compound comprises hydrophobic granule.In further embodiment, described hydrophobic particle serves as pik woods emulsifying agent and contains silica dioxide granule, clay, oxide compound, polymer beads, or their combination.
In one embodiment, the particle diameter of described coating particles is 10 nanometers to 200 micron.In further embodiment, the particle diameter of described coating particles is 10 nanometers to 10 micron.In yet another embodiment, the particle diameter of described coating particles is that 100 nanometers are to 5 microns.In yet another embodiment, the particle diameter of described coating particles is 5 microns to 200 microns.In another embodiment, the composition provided also comprises at least one tensio-active agent.In another embodiment, the composition provided does not comprise tensio-active agent.In another embodiment, described at least one tensio-active agent comprises anion surfactant, nonionogenic tenside, or their combination.In further embodiment, described at least one tensio-active agent comprises ionic surface active agent, and it is selected from vitriol, sulfonate, and their combination.In yet another embodiment, described at least one tensio-active agent comprises nonionogenic tenside, and it is selected from by fatty alcohol ethoxylate, fatty acid ethoxylate, polyoxyethylene and polyolefinic segmented copolymer, and the group of their combination composition.In another embodiment, the ratio of activeconstituents and resinous substrates is about 1:1 to about 1:100.In another embodiment, the ratio of activeconstituents and resinous substrates is about 1:2 to about 1:100.In another embodiment, the ratio of activeconstituents and resinous substrates is at least 1:1.In another embodiment, the ratio of activeconstituents and resinous substrates is less than 1:100.
In yet another aspect, provide a kind of method for the preparation of composition, comprise,
A activeconstituents mixes at the temperature higher than described melting point resin with resin by ();
B the miscellany of step (a) is distributed in the oily medium containing hydrophobic particles by (); With
C () solidifies pik woods particle by the temperature be cooled to lower than described melting point resin.
In one embodiment, described oily medium comprises the mixture of the alkane of C14 to C50, or petroleum distillate.In another embodiment, described oily medium comprises mineral oil, light mineral oil, Isopar oil, Unipar oil and other hydrocarbon ils, edible oil, or their combination.In another embodiment, the temperature lower than described melting point resin is envrionment temperature.In another embodiment, the ratio of pik woods particle and oily medium is about 1:5 to about 1:25.In another embodiment, the ratio of pik woods particle and oily medium is from about 1:10 to about 1:24.In another embodiment, the ratio of described resinous substrates and oily medium is about 2:1 to about 1:100.In another embodiment, the ratio of described resinous substrates and oily medium is about 1:1 to about 1:100.In another embodiment, the ratio of described activeconstituents and resinous substrates is about 1:1 to about 1:100.In another embodiment, the ratio of described activeconstituents and resinous substrates is about 1:2 to about 1:100.In another embodiment, the ratio of described activeconstituents and resinous substrates is at least 1:1.In another embodiment, the ratio of described activeconstituents and resinous substrates is less than 1:100.
In yet another aspect, provide a kind of slurry containing the set of aqueous medium and coating particles, wherein, each described coating particles comprises,
A () is dispersed in the activeconstituents in resinous substrates; With
B () comprises at least one hydrophobic compound coating.
In the embodiment of a slurry provided, activeconstituents comprises volatile compound.In further embodiment, volatile compound comprises cyclopropylene.In further embodiment, described cyclopropylene comprises 1-methylcyclopropene (1-MCP).In another embodiment, activeconstituents comprises the mixture containing cyclopropylene and molecular encapsulation agent.In further embodiment, described molecular encapsulation agent comprises alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin, or their combination.In another embodiment, pulp bales is containing composition provided in this article.
In yet another aspect, provide a kind of method processing plant or plant part, comprise the slurry making described plant or plant part contact comprise aqueous medium and coating particles set, wherein, each described coating particles comprises:
A () is dispersed in the activeconstituents in resinous substrates; With
B () comprises at least one hydrophobic compound coating.
In the embodiment of a method provided, activeconstituents comprises volatile compound.In further embodiment, volatile compound comprises cyclopropylene.In further embodiment, described cyclopropylene comprises 1-methylcyclopropene (1-MCP).In another embodiment, activeconstituents comprises the mixture containing cyclopropylene and molecular encapsulation agent.In further embodiment, described molecular encapsulation agent comprises alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin, or their combination.In another embodiment, the method uses composition provided by the invention.
Accompanying drawing explanation
Fig. 1 shows the representative coatings particle of composition provided herein, represents the pik woods rock steady structure using hydrophobic particles.HAIP refers to the mixture of 1-methylcyclopropene/alpha-cylodextrin.
Fig. 2 shows 1-methylcyclopropene (1-MCP) representative release profiles.Fig. 2 A shows the rate of release of HAIP in water at ambient temperature.Fig. 2 B shows emulsification HAIP and the oil-in-water of 30 minutes at different temperatures.
Under Fig. 3 shows envrionment temperature, when dilute with water, the representative release profiles of the 1-MCP of different time sample #1 and sample #2: Fig. 3 A is 5-360 minute; Be 5-4200 minute with Fig. 3 B.
Under Fig. 4 shows envrionment temperature, when dilute with water, the representative release profiles of the 1-MCP of different time sample #5: Fig. 4 A is 5-360 minute; Fig. 4 B is at 5-1100 minute.
When Fig. 5 shows dilute with water, the representative release profiles of the 1-MCP of sample #3 and sample #4: Fig. 5 A is under room temperature 5-360 minute; Fig. 5 B is under room temperature 5-4000 minute; With Fig. 5 C be 70 degrees Celsius lower 30 minutes.
Fig. 6 shows sample #1 (Fig. 6 a, 6b and 6c), sample #2 (Fig. 6 d, 6e and 6f); With the representative SEM image of sample #4 (Fig. 6 g, 6h and 6i).
Detailed Description Of The Invention
Provide the method for the preparation of composition, comprising: activeconstituents (such as, the powder of 1-MCP mixture) mixes with resin by (1) at just over the temperature of this melting point resin; (2) by shearing in the oily medium that to be distributed to by this mixture containing hydrophobic particles, and oil dispersion liquid is obtained; (3) by this resin particle of cooling curing.Therefore, described activeconstituents (such as, 1-MCP composite powder) is embedded in resinous substrates ball, and described hydrophobic particle, it also serves as pik woods (Pickering) emulsifying agent to stablize this matrix ball, forms coating around this matrix ball to provide waterproof.Therefore, this ball is made up of " pik woods " particle and resinous substrates, embeds activeconstituents wherein.
Additionally provide the composition using method provided herein to prepare.The representative pattern of the ball of the method manufacture provided is shown in Fig. 1.Due to samples with water dilution, water needs through hydrophobic coating and penetrates in resinous substrates, with embed active ingredient (such as, 1-MCP composite powder) interact, and from mixture release of active ingredients (such as, 1-MCP).Therefore, compared with unprotected (or uncoated) 1-MCP composite powder, during dilute with water, the 1-MCP release of comparatively delaying can be realized.This also makes 1-MCP uniform delivery to plant, use effective with consistent under allowing field conditions, and provides significant improvement in regulating plant physiology.
Suitable oily medium can comprise mineral oil, and it can comprise the light compounds of the alkane in C15 to C40 scope, or petroleum distillate.Suitable oil includes, but not limited to mineral oil, light mineral oil, Isopar oil, Unipar oil and other hydrocarbon ils, edible oil and their mixture.
Suitable vibrin comprises polycaprolactone polyol.Typical molecular weight can be 1,000 to 200, and 000; From 2000 to 50000; From 2000 to 8000; Or from 2000 to 4000.Typically, the fusing point of this polycaprolactone polyol is from 30 degrees Celsius to 120 degrees Celsius; From 40 degrees Celsius to 80 degrees Celsius; Or from 50 degrees Celsius to 60 degrees Celsius.Such as, comprise molecular weight about 120, the resin of the PCL of 000 can have the fusing point of about 60 degrees Celsius.In one embodiment, this resin with 60 degrees Celsius of fusing points is useful to theme of the present invention.Known 1-methylcyclopropene/alpha-cylodextrin mixture (HAIP) can short period of time (such as four minutes) tolerable temperature about 100 degrees Celsius and losing without remarkable activity.In one embodiment, technological temperature a little more than the fusing point of resin and the treatment time be less than 20 minutes.
Suitable hydrophobic compound or hydrophobic particle comprise water drain silica, and wherein silica sphere is by silane coupling agent or organic-silicon-modified.Primary particle sizes can be about 10 nanometers to several microns.
Suitable resin is not limited to the pure polymer resin with identical chemical structure or same molecular amount, also can comprise the blend of several resin.Be suitable for use in resin types of the present invention and include, but not limited to polyester, polyethers, epoxy resin, isocyanic ester, ethylene vinyl acetate copolymer, the wax of natural or synthesis, and their mixture.But at least one composition in these resins and HAIP have relative strong interaction, so that HAIP particle can be retained in resinous substrates.In one embodiment, resin has the fusing point lower than 100 degrees Celsius, and lower than 10, the viscosity of 000 centipoise, so that it can mix with HAIP powder, and is distributed in oil medium easily.
The hydrophobic particle be applicable in the present invention as pik woods emulsifying agent includes, but not limited to silica dioxide granule, clay, oxide compound, polymer beads and their mixture.On the other hand, conventional tensio-active agent is optional, to assist the formation of the stable suspension of particle in oil.Suitable tensio-active agent comprises, such as, and anion surfactant, nonionogenic tenside, and their mixture.Some suitable anion surfactants include, but not limited to vitriol and sulfonate.Some suitable nonionogenic tensides include, but not limited to the ethoxylate of fatty alcohol, the ethoxylate of lipid acid, polyoxyethylene and polyolefinic segmented copolymer, and composition thereof.
The step being suitable for being used in cured granulate of the present invention includes, but not limited to be cooled to envrionment temperature.Pik woods particle powder can be about 1:5 to about 1:25 with the ratio of oil; Or from about 1:10 to about 1:24.The ratio of described HAIP powder and resin can be about 1:1 to 1:100; Or from about 1:2 to about 1:100.Resin can be about 2:1 to about 1:100 with the ratio of oil; Or from about 1:1 to about 1:100.
As used herein term " polymer " " refer to the relatively large molecule be made up of the reaction product of less chemical repeat unit.Repeating unit (also referred to as " monomeric unit ") is the residue of monomer molecule.Described repeating unit can be all identical, or can comprise two or more different repeating units.Polymer molecule can have any structure, such as, straight chain, side chain, star, crosslinked, and their mixture.Polymericular weight can be measured by standard method, such as, and size exclusion chromatography, (SEC, also referred to as gel permeation chromatography or GPC).Polymkeric substance has the number-average molecular weight (Mn) being greater than 700." oligopolymer " molecule of being made up of the reaction product of the less chemical repeat unit being called monomeric unit as used herein.Oligopolymer has the molecular weight of 700 or less.
Thermosetting polymer can be cross-linked completely.Thermosetting polymer is not molded into new shape by heating and applying pressure, and thermosetting polymer is insoluble in any solvent.The polymkeric substance of not thermosetting is called as thermoplastic polymer.
As used herein, if at 25 DEG C, a kind of material soluble is less than 1 gram every 100 grams of water in the amount of substance of water, then this material is water-fast.
As used herein, when mentioning the set of powder particle, phrase " most or whole powder particle " refers to the powder particle of 50% to 100%, based on the gross weight of the set of described powder particle.
As used herein, " solvated compounds " is under a barometric point, the compound of boiling point between 20 DEG C and 200 DEG C, and at one atm, is liquid in the temperature range comprising 20 DEG C to 30 DEG C." solvent " can be solvated compounds or solvent mixture.Non-aqueous solvent can not be or moisture or based on the weight of solvent, the solvent of moisture less than 10%.
As used herein, phrase " aqueous medium " refers to a kind of composition, and it is liquid at 25 DEG C, and based on the weight of aqueous medium, the water containing 75% (weight) or more.The composition be dissolved in aqueous medium is all considered to a part for aqueous medium, but the material being insoluble to aqueous medium is not considered to a part for aqueous medium.If a kind of individual molecule of composition to be distributed in whole liquid and to be contact with the molecule in close of liquid, then this composition in a liquid " dissolving ".
As used in this article, when mentioning that arbitrary ratio is X:1 or higher, this ratio is Y:1, and wherein Y is X or higher.Similarly, when mentioning that any ratio is R:1 or lower, this ratio refers to as S:1, and wherein S is R or lower.
As used herein, " aspect ratio " of solid particulate is the ratio of the longest dimension of particle and the shortest size of this particle.The longest dimension of particle is through the length of the possible nose section (" line segment L ") of the mass center of particle, and its each end points is all on the surface of particle.The shortest size of this particle is through the length of the possible line of shortest length section (" line segment S ") of the mass center of particle, and its each end points is all on the surface of particle, and it is perpendicular to line segment L.Aspect ratio is the ratio of the length of line segment L and the length of line segment S.
As used herein, " diameter " of particle is the mean value of the length of the line segment L of this particle and the line segment S of this particle, it is noted that when described particle is spherical, and this defines " diameter " that give on ordinary meaning.
As used herein, when an attribute of powder is described to have " centre " value, can be expected that, the half of the cumulative volume of described powder particle by by the half had higher than the granulometric composition of this property value and the cumulative volume of described powder particle by by the granulometric composition had lower than this property value.
Enforcement of the present invention comprises one or more compound cyclopropenes of use.As used herein, compound cyclopropene is any compound with following formula structure:
The wherein group that forms independently selected from the chemical group by H and following formula of each R1, R2, R3 and R4:
-(L)
n-Z
Wherein n is the integer from 0 to 12.Each L is all divalent groups.Suitable L group comprises, such as, containing being selected from H, and the group of one or more atoms of B, C, N, O, P, S, Si or their mixture.Atom in L group by singly-bound, double bond, triple bond, or their mixture is connected to each other.Each L group can be straight chain, side chain, ring-type, or their combination.At any one R group (that is, R
1, R
2, R
3and R
4in any one) in, heteroatomic sum (that is, except the atom of H and C) is 0 to 6.Independently, in any one R group, the sum of non-hydrogen atom is 50 or less.Each Z is univalent perssad.Each Z is independently selected from hydrogen, and halogen, cyano group, nitro, nitroso-group, azido-, chlorate anions, bromate, iodate, isocyano, isocyanido, isosulfocyanate radical, five fluorine sulfenyls, and chemical group G, wherein G is the loop systems of 3 to 14 yuan.
R
1, R
2, R
3and R
4group is independently selected from suitable group.Be suitable as one or more R
1, R
2, R
3and R
4group be, such as, aliphatic group, aliphatic oxygen groups, alkylphosphonato base, cycloaliphatic radical, naphthene sulfamide group, cycloalkyl amino, heterocyclic radical, aryl, heteroaryl, halogen, silyl, other group, and their mixture and combination.Be suitable as one or more R
1, R
2, R
3and R
4group can be substituted or unsubstituted.
Suitable R
1, R
2, R
3and R
4group be, such as, aliphatic group.Some suitable aliphatic groups comprise, such as, and alkyl, thiazolinyl and alkynyl.Suitable aliphatic group can be straight chain, side chain, ring-type, or their combination.Independently, suitable aliphatic group can be replacement or unsubstituted.
As used herein, if one or more hydrogen atoms of the chemical group paid close attention to are substituted with a substituent, then paid close attention to chemical group is said to be " replacement ".
Suitable R
1, R
2, R
3and R
4group is, such as, replaces and unsubstituted heterocyclic group, and it is by middle oxygen base, and amino, carbonyl or alkylsulfonyl are connected in compound cyclopropene; Such R
1, R
2, R
3and R
4the example of group is heterocyclic oxy group, heterocyclic radical, two heterocyclylamino group (diheterocyclylamino) and two heterocyclylamino group alkylsulfonyl diheterocyclylaminosulfonyl.
Suitable R
1, R
2, R
3and R
4group is, such as, replaces and unsubstituted heterocyclic group, and it is amino by middle oxygen base, carbonyl, alkylsulfonyl, sulfanyl (thhioalkyl group), or amino-sulfonyl is connected in compound cyclopropene; Such R
1, R
2, R
3and R
4the example of group is two heteroaryl aminos (diheteroarylamino), heteroaryl sulfanyl (heteroarylthioalkyl), and two heteroarylaminosulfonyl (diheteroarylaminosulfonyl).
In addition, suitable R
1, R
2, R
3and R
4group is, such as, and hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, nitroso-group, azido-, chlorato, bromato, iodato, isocyanato, isocyanido, different sulphur, five fluorine; Acetoxyl group, ethoxycarbonyl, cyanogen, nitrate radical, nitrito, perchlorato, propadiene base, butylmercapto, diethyl phosphine (diethylphosphonato), dimethylphenylsilaneand, isoquinoline 99.9, sulfydryl, naphthyl, phenoxy group, phenyl, piperidino-(1-position only), pyridyl, quinolyl, triethyl-silicane, trimethyl silyl; With the analogue of their replacement.
As used herein, chemical group G is 3 to 14 membered ring system.That the loop systems being suitable as chemical group G replaces or unsubstituted; They can be aromatics (comprising such as phenyl and naphthyl) or aliphatic series (comprise undersaturated aliphatic series, the aliphatic series of fractional saturation, or radical of saturated aliphatic base); They can be carbocyclic ring or heterocycle.In the G group of heterocycle, some suitable heteroatomss are such as nitrogen, sulphur, oxygen, and their combination.The member ring systems being suitable as chemical group G can be monocycle, dicyclo, three rings, many rings, volution, or condensed ring; In the member ring systems of suitable chemical group G, it is dicyclo, and in three rings or condensed ring, each ring in single chemical group G can be all identical types, or can be two or more type (such as, aromatic ring can condense with aliphatics ring).
In one embodiment, one or more R
1, R
2, R
3and R
4hydrogen or (C
1-C
10) alkyl.In another embodiment, each R
1, R
2, R
3and R
4hydrogen or (C
1-C
8) alkyl.In another embodiment, each R
1, R
2, R
3and R
4hydrogen or (C
1-C
4) alkyl.In another embodiment, each R
1, R
2, R
3and R
4hydrogen or methyl.In another embodiment, R
1(C
1-C
4) alkyl and each R
2, R
3and R
4hydrogen.In another embodiment, R
1be methyl and each R
2, R
3and R
4be hydrogen, and compound cyclopropene is 1-methylcyclopropene or " 1-MCP " in this article.
In one embodiment, operable compound cyclopropene boiling point is at one atm 50 DEG C or lower; 25 DEG C or lower; Or 15 DEG C or lower.In another embodiment, operable compound cyclopropene boiling point is at one atm-100 DEG C or higher;-50 DEG C or higher;-25 DEG C or higher; Or 0 DEG C or higher.
Composition of the present invention comprises at least one molecular encapsulation agent.In preferred embodiments, at least one molecular encapsulation agent encapsulates a part for one or more compound cyclopropenes or one or more compound cyclopropenes.The mixture comprising a part for compound cyclopropene molecule or compound cyclopropene molecule be encapsulated in molecular encapsulation agent molecule is called as " compound cyclopropene mixture " in this article.
In one embodiment, at least one compound cyclopropene mixture is inclusion complex.In the further embodiment of such inclusion complex, described molecular encapsulation agent forms cavity, and a part for described compound cyclopropene or compound cyclopropene is in cavity.
In another this inclusion complex embodiment, the cavity inside of molecular encapsulation agent is nonpolar or hydrophobic substantially or both has, and described compound cyclopropene (or being positioned at the part of compound cyclopropene of this cavity) is also substantially nonpolar or hydrophobicity or both have.Although the invention is not restricted to any specific theory or mechanism, but can be expected that, in so nonpolar compound cyclopropene mixture, Van der Waals force, or hydrophobic interaction, or both, compound cyclopropene molecule or its part are remained in the described cavity of molecular encapsulation agent.
The amount of molecular encapsulation agent can be characterized by the ratio of the molar weight of molecular encapsulation agent with the molar weight of compound cyclopropene effectively.In one embodiment, the molar weight of molecular encapsulation agent can be 0.1 or larger with the ratio of the molar weight of compound cyclopropene; 0.2 or larger; 0.5 or larger; Or 0.9 or larger.In another embodiment, the mol ratio of molecular encapsulation agent and compound cyclopropene can be 10 or lower; 5 or lower; 2 or lower; Or 1.5 or lower.
Suitable molecular encapsulation agent comprises, such as, and organic and inorganic molecule encapsulation agent.Suitable organic molecule encapsulation agent, it comprises, such as, the cyclodextrin of replacement, unsubstituted cyclodextrin, and crown ether.Suitable inorganic molecule encapsulation agent comprises, such as, and zeolite.The mixture of suitable molecular encapsulation agent is also suitable.In one embodiment, encapsulation agent is alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin, or their combination.In further embodiment, use alpha-cylodextrin.
In one embodiment, composite powder can have 10 microns or less, 7 microns or less, or 5 microns or less median particle diameter.In another embodiment, composite powder can have 0.1 micron or more, or the median particle diameter of 0.3 micron or more.Median particle diameter is measured by optical diffraction method commercial instruments, such as, by HoribaCo. or Malvern instrument manufacturing.
In another embodiment, composite powder can have 5:1 or lower; 3:1 or lower; Or the aspect ratio of 2:1 or lower.If the composite powder obtained has undesirable high median aspect ratio, can use mechanism, such as, mill, reducing median aspect ratio is desired value.
In one embodiment, suitable resin can have 55 DEG C or higher; 65 DEG C or higher; Or more than 70 DEG C fusing points.In another embodiment, suitable resin can have 100 DEG C or lower; Or 90 DEG C or lower fusing point.
The other method of assessment fatty compounds is initial (onset) temperature of fusing point.In order to determine starting temperature, the fusing point transition (heat flux and temperature) of the exotherm that observation DSC produces.Determine baseline, and by deducting baseline correction heat flow curve from original heat flow curve.Determine the maximum heat flux values of calibration curve (HFMAX).Described starting temperature is the minimum temperature that heat flow value on calibration curve equals 0.1*HFMAX place.Suitable resin can have 45 DEG C or higher; Or 55 DEG C or higher starting temperature.
Wherein, the useful characteristic manner of powder composition of the present invention is median particle diameter, and it can be 100 microns or less; 75 microns or less; 50 microns or less; Or 25 microns or less.
Composition of the present invention can by any way for the treatment of plant or plant part.Such as, said composition can with other material mixing, or also can directly to use.
The method using composition of the present invention to form aqueous slurry is provided.A kind of aqueous slurry can be formed when provided composition mixes with aqueous medium.For forming such slurry, described aqueous medium can directly mix with composition of the present invention.The coating particles that it is expected to provided composition keeps complete in slurries.It is also contemplated that great majority or whole coating particles disperse as independent particle instead of the aggregate as them in the slurry.Described coating particles may need mechanical agitation to keep suspending in water medium, or they can not stir and keep suspending.
Can being characterized by the concentration of compound cyclopropene in the slurry of amount of composition in these slurries.In one embodiment, the concentration of the compound cyclopropene of suitable slurry can be 2 or higher, 5 or higher; Or 10 or higher, in units of the milligram number of the compound cyclopropene at often liter of slurry.In another embodiment, the concentration of the compound cyclopropene of suitable slurry can be 1000 or lower, 500 or lower, or 200 or lower, in units of the milligram number of the compound cyclopropene at often liter of slurry.
In the water-bearing media that slurry uses, the amount of water can be, based on the weight of water-bearing media, 80% or more; 90% or more; Or 95% or more.
This slurry optionally can contain one or more adjuvants, such as, and one or more metal chelating agents, one or more tensio-active agents, one or more oil, one or more alcohol or their mixture.The example of metal chelating agent, if you are using, comprises sequestrant.The example of tensio-active agent, if you are using, comprises anion surfactant and silicone surfactant.The example of alcohol, if you are using, comprises the alkyl alcohol with 4 or less carbon atoms.Oil is compound, is liquid at 25 DEG C, is not water, is not tensio-active agent, and is not alkylol cpd.The example of oil, if you are using, comprises hydrocarbon ils and silicone oil.
Additionally provide by making slurry contact with plant or plant part and process the method for plant.Such contact can be carried out in any position, comprises closed interior volume (such as, container, room, or buildings) or the outside of enclosed space.In one embodiment, such contact performs outside any enclosed space.As used herein, " outside any enclosed space " refers to the outside of any buildings or casing, or in the room or buildings that arrive outside atmosphere of ventilating.In another embodiment, such contact is that the outside of any buildings or casing is carried out.In further embodiment, such contact carries out in outdoor wild country or field.
Slurry of the present invention can make it contact with plant or plant part by method as known in the art.The example of method comprises plant part is immersed slurry, and by spraying, foaming, brush, or slurry is applied to plant or plant part by their combination.Other example comprises spraying slurry to plant or plant part, and makes plant part dipping sizing agent.Other example comprises jetting slurry and expects plant or plant part.
Can process plant or plant part in the practice of the invention.An example is the whole plant of process; Another example is when planting in soil, the whole plant of pre-treatment of results useful plant part.
The plant of any plant part provided can be processed in the practice of the invention.Example comprises provides fruit, the plant of vegetables and cereal.
As used herein, phrase " plant " comprises dicotyledons and monocotyledons.The example of dicotyledons comprises tobacco, Arabidopsis, soybean, tomato, pawpaw, rape, Sunflower Receptacle, cotton, clover, potato, grape, pigeonpea, pea, rape, garbanzo, beet, rape, watermelon, muskmelon, capsicum, peanut, pumpkin, radish, spinach, pumpkin, Caulis et Folium Brassicae capitatae, Chinese cabbage, Radix Dauci Sativae, Cauliflower, celery, Chinese cabbage, cucumber, eggplant, and romaine lettuce.Monocotyledonous example comprises corn, paddy rice, wheat, sugarcane, barley, rye, Chinese sorghum, orchid, bamboo, banana, cattail, lily, oat, onion, millet and triticale.
As used herein, phrase " plant-growth regulator " includes, but not limited to ethene, cyclopropylene, glyphosate, careless ammonium phosphine, and 2,4-D.Other suitable plant-growth regulator is open in international patent application WO2008/071714A1, and it is incorporated to herein with its entirety by reference.
Embodiment
Embodiment 1
Sample preparation
Step-the sample preparation of preparation 1-MCP powder dispersion is as follows:
A () is loaded into HAIP (1-methylcyclopropene/alpha-cylodextrin mixture) powder and fluoropolymer resin that air-flow grinds in a reservoir, then container is placed in oil bath, and the temperature be heated to a little more than this melting point resin, under shearing force, described HAIP powder is evenly spread in this resin, thus obtains thickness dispersion;
B SiO 2 powder adds in oil by (), then shear at ambient temperature to obtain uniform mixture.Then this mixture is heated to the temperature slightly above melting point resin;
C HAIP powder dispersion in the oil of step (a) adds in the oil of step (b) and the mixture of silica dioxide granule by ().By high speed shear at the temperature of the fusing point of a little higher than described resin, the HAIP powder dispersion in the oil of step (a) is made to be distributed to from the oil of step (b) and the mixture of silica dioxide granule; With
D () is by cooling curing discrete particles.
Embodiment 2
Testing method
Have studied the release of dilute sample in such a way: by being encased in 22 milliliters of bottles of the tensio-active agent of about 0.2g sample and 0.04g, and mixture is even by shear-mixed.Then in bottle, add the water of 2 milliliters, after shearing, obtain the emulsion of milk shape.This method is used to prepare the sample of a series of dilution.After bottle places certain hour at ambient temperature, carry out sample analysis by vapor-phase chromatography, observe the change in concentration of 1-MCP, effective release of go forward side by side line trace and detection 1-MCP.Then close the well heater in stove, the temperature of stove about 40 degrees Celsius, and envrionment temperature is about 22 degrees Celsius.After preset time after samples with water dilution, carry out headspace analysis measurement.Each bottle is sampled once, that is, use new bottle to obtain each data point of time releasing research.
From the measurement concentration of the 1-MCP of headspace, join the sample size in bottle and the theoretical 1-MCP content in sample, the mark of 1-MCP total amount in the bottle remaining in headspace can be calculated, and report with per-cent based on the amount of the 1-MCP joined in bottle.
The 1-MCP release comparing sample discharges with the 1-MCP of HAIP powder.In order to measure the 1-MCP release of HAIP, weighing about 20mgHAIP powder, to join in 22 milliliters of ml headspace bottle and to inject the water of 2ml.Headspace analysis test is carried out under condition same as described above.
Embodiment 3
Prepared by sample #1
Prepare sample #1 as follows:
(1) join in container by 26.04 grams of vibrin, this container is heated to the fusing point of this polyester, that is, 60 degrees Celsius.After all resin meltings, be loaded into 6.47 grams of HAIP powder, and mixture fully mixed in about ten minutes by shearing, then HAIP powder is evenly dispersed in the resin of melting, obtains the dispersion of thickness.
(2) 64.45 grams of mineral oil and 3.04 grams of SiO 2 powders load in container, then fully being mixed by mixture by shearing, being then heated to 60 degrees Celsius.
(3) at about 60 degrees Celsius, under the high-shear of about 1000rpm, HAIP dispersion (1) is mixed about three minutes with pik woods particle dispersion (2); Resin is dispersed in mineral oil to form the ball wherein embedding HAIP.Then dispersion liquid is cooled to envrionment temperature.
Embodiment 4
Prepared by sample #2
Prepare sample #2 as follows:
(1) join in container by 28.75 grams of vibrin, this container is heated to the fusing point of this polyester, that is, 60 degrees Celsius.After all resin meltings, load 7.19 grams of HAIP powder, and within about ten minutes, fully mixed by mixture by shearing, then HAIP powder is evenly dispersed in the resin of melting, obtains the dispersion of thickness.
(2) 60.15 grams of mineral oil and 3.91 grams of SiO 2 powders are loaded in container, then fully being mixed by shearing by mixture, being then heated to 60 degrees Celsius.
(3) at about 60 degrees Celsius, under the high-shear of about 3400rpm, HAIP dispersion (1) is mixed about three minutes with pik woods particle dispersion (2); Resin is dispersed in mineral oil to form the ball wherein embedding HAIP.Then dispersion liquid is cooled to envrionment temperature.
Embodiment 5
Prepared by sample #3
Prepare sample #3 as follows:
(1) 22.98 gram of vibrin joins in container, and this container is heated to the fusing point of this polyester, that is, 60 degrees Celsius.After all resin meltings, load 5.74 grams of HAIP powder, and within about ten minutes, fully mixed by mixture by shearing, then HAIP powder is evenly dispersed in the resin of melting, obtains the dispersion of thickness.
IsoparM and the 4.27 gram SiO 2 powder of (2) 67.01 grams is loaded in container, then fully being mixed by mixture by shearing, being then heated to 60 degrees Celsius.
(3) at about 60 degrees Celsius, under the high-shear of about 3400rpm, HAIP dispersion (1) is mixed about three minutes with pik woods particle dispersion (2); Resin is dispersed in IsoparM to form the ball wherein embedding HAIP.Then dispersion liquid is cooled to envrionment temperature.
Embodiment 6
Prepared by sample #4
Prepare sample #4 as follows:
(1) 23.27 gram of vibrin joins in container, and this container is heated to the fusing point of this polyester, that is, 60 degrees Celsius.After all resin meltings, load 5.83 grams of HAIP powder, and within about ten minutes, fully mixed by mixture by shearing, then HAIP powder is evenly dispersed in the resin of melting, obtains the dispersion of thickness.
The IsoparM of (2) 65.85 grams, 4.20 grams of silicon-dioxide R805 and 0.85 gram of D17 powder load in container, then fully being mixed by mixture by shearing, being then heated to 60 degrees Celsius.
(3) at about 60 degrees Celsius, under the high-shear of about 3400rpm, HAIP dispersion (1) is mixed about three minutes with pik woods particle dispersion (2); Resin is dispersed in IsoparM to form the ball wherein embedding HAIP.Then dispersion liquid is cooled to envrionment temperature.
Embodiment 7
Prepared by sample #5
Prepare sample #5 as follows:
(1) 22.88 gram of vibrin joins in container, and this container is heated to the fusing point of this polyester, that is, and 60 degrees Celsius.After all resin meltings, load 5.72 grams of HAIP powder, and within about ten minutes, fully mixed by mixture by shearing, then HAIP powder is evenly dispersed in the resin of melting, obtains the dispersion of thickness.
(2) 67.37 grams of mineral oil, 0.81 gram of Unithox, 720,1.88 grams of Unithox 750 and 1.34 grams of SDBS load in container, then mixture are heated to about 110 degrees Celsius.After this, mixture is sheared fully to mix, and is then cooled to 60 degrees Celsius to obtain surfactant dispersion.
(3) at about 60 degrees Celsius, HAIP dispersion (1) and surfactant-dispersed liquid (2) about three minutes under high-shear, is mixed; Resin is dispersed in mineral oil to form the particle wherein embedding HAIP particle.Then by dispersion liquid cool to room temperature.
Embodiment 8
Formula
The Formulation Summary of sample in Table 1.
Embodiment 9
Comparative sample
Comparative sample is prepared as follows:
(1) HAIP+ water system: 20 milligrams of HAIP powder-tights in the vial, and inject 2ml water, by the 1-MCP concentration of gas chromatographic analysis headspace.Fig. 2 A to show when contacting with water 1-MCP from the release profiles HAIP powder.As shown in Figure 2 A, at ambient temperature, 1-MCP discharges, and spreads completely from HAIP after contacting about ten minutes with water.
HAIP+ oil+water system: first use to shear and oily to be mixed with 250 milligrams by 20 milligrams of HAIP powder, then seals this mixture and tensio-active agent in the vial, and injects water, then by bottle jolting to obtain uniform emulsion.After this, in different temperature (22,50,55,60,65 and 70 DEG C), the sample of dilution is kept 30 minutes.By the 1-MCP concentration of gc analysis headspace at corresponding temperature.Fig. 2 B shows the release profiles of 1-MCP.As shown in Figure 2 B, after emulsification sample remain on 22,50,55,60,65 and 70 degrees Celsius 30 minutes, the 1-MCP being discharged into headspace is respectively 70%, 80%, 84%, 91%, 95% and 100%.That is, with the rising of temperature, this fractional release raises, and under existence conditions, only has the 1-MCP of 70% to be discharged in headspace when envrionment temperature, even and if sample keeps the longer time at such a temperature, and fractional release remains ~ and 70%.
Embodiment 10
The release overview of test sample
Fig. 3 A shows the 1-MCP release profiles of the sample #1 of dilution and the representative of sample #2.As shown in Figure 3A, initial release is than being ~ 4% (sample #1) and ~ 10% (sample #2); In 300 minutes, release rate does not have large change, is less than 10% for sample #1, and for sample #2 about 20%.For the longer time, as shown in Figure 3 B, As time goes on, release rate increases, even if contact as after about 4000 minutes with water, and 1-MCP or sustained release.
Fig. 4 A shows the representative 1-MCP release profiles of the sample #5 of dilution.As shown in Figure 4 A, initial release ratio is ~ 25%; Within 5-300 minute, release rate from large ~ 25% be increased to ~ 41%.For the longer time, as shown in Figure 4 B, As time goes on, release rate increases, even if contact as after about 1100 minutes with water, and 1-MCP or sustained release.
Fig. 5 A and 5B shows the 1-MCP release profiles of the sample #3 of dilution and the representative of sample #4.As shown in Figure 5 A and 5B, in 240 minutes, the releasing ratio of two samples is about 23%, and fractional release does not have wide variation.For the longer time, as shown in Figure 5 B, As time goes on, release rate increases, even if contact as after about 4000 minutes with water, and 1-MCP or sustained release.As shown in Figure 5 C, kept 30 minutes at 70 degrees Celsius by the sample of this dilution, fractional release is about 88.7% (sample #3), 85.1% (sample #4).
In view of the above circumstances, the composition of matrix encapsulation of the present invention is convenient to use in liquid form.Compare HAIP powder type, HAIP particle is by resinous substrates ball and the duplicate protection according to the hydrophobic pik woods layer around the ball of provided component.When samples with water is diluted, water needs through hydrophobic granule layer and penetrates in resinous substrates, with the HAIP Interaction between particles embedded, and discharges 1-MCP from HAIP.Lower initial release ratio can be realized in several hours after dilution, the 1-MCP slow releasing of longer time can be realized, and obtain longer duration of service; And this allows the uniform delivery of 1-MCP after thin up, use effective with consistent under allowing condition in the wild.Compare oil droplet encapsulation preparation, wherein, because 1-MCP gas is used, the content of 1-MCP is very low (being less than 50ppm), because HAIP powder can encapsulate in the present invention, the content of 1-MCP can increased to over 200,000 ppm.
Embodiment 11
The SEM image of laboratory sample
The SEM image of described dispersion can be obtained to test sample provided in this article.As shown in Figure 6, sample #1, the particle diameter of sample #2 and sample #4 is about 30-250 micron respectively, 20-100 micron, and 20-120 micron.In addition, for all these samples, described matrix ball is covered by hydrophobic silica particulate.For the research of 1-MCP release performance, sealed sample and some tensio-active agents in the vial, and inject water, then by bottle jolting to obtain uniform emulsion.After preset time after dilution, carry out headspace analysis measurement.
Claims (35)
1. a composition, it comprises the set of coating particles, and wherein each described coating particles comprises:
A () is dispersed in the activeconstituents in resinous substrates; With
B () comprises the coating of at least one hydrophobic compound.
2. composition as claimed in claim 1, wherein said activeconstituents comprises volatile compound.
3. composition as claimed in claim 2, it is rare that wherein said volatile compound comprises ring third.
4. composition as claimed in claim 3, wherein said ring third is rare comprises 1-methylcyclopropene (1-MCP).
5. composition as claimed in claim 1, wherein said activeconstituents comprises the mixture containing cyclopropylene and molecular encapsulation agent.
6. composition as claimed in claim 5, wherein said molecular encapsulation agent comprises alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin, or their combination.
7. composition as claimed in claim 1, wherein said activeconstituents comprises plant-growth regulator.
8. composition as claimed in claim 1, wherein said resinous substrates comprises vibrin.
9. composition as claimed in claim 1, wherein said resinous substrates comprises polyester, polyethers, epoxy resin, isocyanic ester, ethylene vinyl acetate copolymer, the wax of natural or synthesis or their combination.
10. composition as claimed in claim 1, wherein said resinous substrates comprises polycaprolactone polyol.
11. compositions as claimed in claim 1, the molecular weight that wherein said polycaprolactone polyol has is 1,000 to 200,000.
12. compositions as claimed in claim 1, the fusing point of wherein said polycaprolactone polyol is from 30 degrees Celsius to 120 degrees Celsius.
13. compositions as claimed in claim 1, wherein said at least one hydrophobic compound comprises hydrophobic silica.
14. as the composition of claim 12, wherein by the silica sphere of hydrophobic silica described in silane coupling agent or organosilicon modifier modification.
15. compositions as claimed in claim 1, wherein said at least one hydrophobic compound comprises hydrophobic particle.
16. as the composition of claim 15, and wherein said hydrophobic particle serves as pik woods emulsifying agent and containing silica dioxide granule, clay, oxide compound, polymer beads, or their combination.
17. compositions as claimed in claim 1, the particle diameter of wherein said coating particles is 10 nanometers to 200 micron.
18. compositions as claimed in claim 1, the particle diameter of wherein said coating particles is that 100 nanometers are to 5 microns.
19. compositions as claimed in claim 1, it also comprises at least one tensio-active agent.
20. compositions as claimed in claim 1, wherein said composition does not comprise tensio-active agent.
21. as the composition of claim 19, and wherein said at least one tensio-active agent comprises anion surfactant, nonionogenic tenside, or their combination.
22. as the composition of claim 20, and wherein said at least one tensio-active agent comprises ionic surface active agent, and it is selected from vitriol, sulfonate, and their combination.
23. as the composition of claim 20, and wherein said at least one tensio-active agent comprises nonionogenic tenside, and it is selected from fatty alcohol ethoxylate, fatty acid ethoxylate, polyoxyethylene and polyolefinic segmented copolymer, and their combination.
24. compositions as claimed in claim 1, the ratio of wherein said activeconstituents and described resinous substrates is about 1:1 to about 1:100.
25. compositions as claimed in claim 1, the ratio of wherein said activeconstituents and described resinous substrates is about 1:2 to about 1:100.
26. 1 kinds of methods preparing composition, comprise,
A activeconstituents mixes at the temperature higher than described melting point resin with resin by ();
B the miscellany of step (a) is distributed in the oily medium containing hydrophobic granule by (); With
C () solidifies pik woods particle by the temperature be cooled to lower than described melting point resin.
27. as the method for claim 26, and wherein said oily medium comprises the mixture of the alkane of C14 to C50, or petroleum distillate.
28. as the method for claim 26, and wherein said oily medium comprises mineral oil, light mineral oil, Isopar oil, Unipar oil and other hydrocarbon ils, edible oil, or their combination.
29. as the method for claim 26, and the wherein said temperature lower than described melting point resin is envrionment temperature.
30. as the method for claim 26, and the ratio of wherein said pik woods particle and described oily medium is about 1:5 to about 1:25.
31. as the method for claim 26, and the ratio of wherein said pik woods particle and described oily medium is about 1:10 to about 1:24.
32. as the method for claim 26, and the ratio of wherein said resinous substrates and described oily medium is about 2:1 to about 1:100.
33. as the method for claim 26, and the ratio of wherein said resinous substrates and described oily medium is about 1:1 to about 1:100.
The slurry of 34. 1 kinds of set containing aqueous medium and coating particles, wherein, each described coating particles comprises:
A () is dispersed in the activeconstituents in resinous substrates; With
B () comprises the coating of at least one hydrophobic compound.
35. 1 kinds of methods processing plant or plant part, comprise the slurry making described plant or plant part contact comprise aqueous medium and coating particles set, wherein, each described coating particles comprises:
A () is dispersed in the activeconstituents in resinous substrates; With
B () comprises the coating of at least one hydrophobic compound.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| PCT/CN2012/081468 WO2014040288A1 (en) | 2012-09-17 | 2012-09-17 | Compositions with hot melt resin matrix |
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| RU2015114138A (en) * | 2012-09-17 | 2016-11-10 | Агрофреш Инк. | SUSPENSION OF PARTICLES CONTAINING CYCLOPROPENE COMPLEXES DISPERSED IN RESIN MATRIX |
| BR112020021737A2 (en) | 2018-04-27 | 2021-01-26 | Fresh Inset S.A. | compositions and articles comprising 1-methylcyclopropene and alpha-cyclodextrin complexes |
| CA3170106A1 (en) | 2020-02-03 | 2021-08-12 | Fresh Inset S.A. | Stable 1-methylcyclopropene compositions and uses thereof |
| US20210331990A1 (en) * | 2020-04-27 | 2021-10-28 | Cellresin Technologies, Llc | Compositions and Methods for Differential Release of 1-Methylcyclopropene |
| CN112661977B (en) * | 2020-12-18 | 2022-05-17 | 湖南林特科技有限公司 | Preparation method of water-based aldehyde ketone resin emulsion |
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| CN102217671A (en) * | 2011-04-27 | 2011-10-19 | 武汉双奇科技发展有限公司 | 1-methyl cyclopropene slow release formulation and preparation method thereof |
| WO2011156388A1 (en) * | 2010-06-07 | 2011-12-15 | Syngenta Participations Ag | Cyclopropene compositions |
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| WO2008089140A1 (en) * | 2007-01-17 | 2008-07-24 | Dow Agrosciences Llc | Delivery of ethylene blocking and/or promoting agents |
| BRPI1006175B8 (en) * | 2009-01-09 | 2020-12-08 | Syngenta Participations Ag | composition concentrated in physically stable non-aqueous liquid dispersion |
| EP2563744A4 (en) * | 2010-04-28 | 2017-06-28 | Syngenta Participations AG | Stabilized agrochemical composition |
| CA2743758C (en) * | 2010-07-02 | 2013-01-08 | Rohm And Haas Company | Coated powder particles |
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- 2012-09-17 WO PCT/CN2012/081468 patent/WO2014040288A1/en active Application Filing
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- 2012-09-17 EP EP12884523.7A patent/EP2895541A4/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011156388A1 (en) * | 2010-06-07 | 2011-12-15 | Syngenta Participations Ag | Cyclopropene compositions |
| CN102217671A (en) * | 2011-04-27 | 2011-10-19 | 武汉双奇科技发展有限公司 | 1-methyl cyclopropene slow release formulation and preparation method thereof |
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| IL237308A0 (en) | 2015-04-30 |
| JP2015531417A (en) | 2015-11-02 |
| SG11201501813RA (en) | 2015-04-29 |
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| AR092415A1 (en) | 2015-04-22 |
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| AU2012389722A2 (en) | 2015-03-26 |
| EP2895541A1 (en) | 2015-07-22 |
| BR112015005568A2 (en) | 2017-07-04 |
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