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    • 专利摘要:
    cyclopropene compositions. stabilized liquid cyclopropene compositions comprising fluid non-aqueous concentrated dispersions comprising a) a substantially water-immiscible liquid continuous phase and b) a dispersed solid phase comprising cured polymeric particles prepared from a polymerizable thermoset resin The particles contain at least one cliclopropene complex, optionally a nonporous particulate mineral and optionally a non-crosslinkable mobile chemical distributed therein and wherein the outer surfaces of the particles comprise a solid colloidal material. The compositions of the invention may be used directly or diluted to control pests or as plant growth regulators.
    公开号:BR112012031081B1
    申请号:R112012031081-0
    申请日:2011-06-07
    公开日:2018-05-29
    发明作者:David Fowler Jeffrey；Kim Sejong
    申请人:Syngenta Participations Ag；
    IPC主号:
    专利说明:

    (54) Title: CYCLOPROPEN COMPOSITIONS, THEIR PREPARATION PROCESS, AND METHOD FOR REGULATING PLANT GROWTH (51) Int.CI .: A01N 27/00; A01N 25/02; A01N 25/04 (52) CPC: A01N 27/00, A01N 25/02, A01N 25/04 (30) Unionist Priority: 06/07/2010 US 61 / 352,252 (73) Holder (s): SYNGENTA PARTICIPATIONS AG ( 72) Inventor (s): JEFFREY DAVID FOWLER; SEJONG KIM
    1/39
    Descriptive Report of the Invention Patent for CYCLOPROPEN COMPOSITIONS, THEIR PREPARATION PROCESS, AND METHOD FOR REGULATING PLANT GROWTH.
    [001] The present invention relates to cyclopropene compositions for regulating plant growth, the preparation of such compositions and methods for regulating plant growth using these compositions.
    BACKGROUND OF THE INVENTION [002] Ethylene is known to be involved in plant senescence and plant reactions to stress. For this reason, plant growth regulators (PGRs) that inhibit or regulate ethylene production or control its action on plants have been developed in an effort to improve the economic yield of agricultural crops.
    [003] In practice, such PGRs can be applied to plants using a variety of methods that include different formulations. Of these various methods, the use of liquid and dry compositions is the most common. The specific formulation desired and the resulting effect on the physiology of plant growth will largely depend on the PGR used, the species of plant to be treated, environmental conditions, the geographical area and the climate of the region at the time of treatment. [004] Certain obstacles make the use of some PGRs impractical in some circumstances. For example, a group of PGRs that are ethylene inhibitors are cyclopropenes that are mainly small gas molecules. An example of such a cyclopropene PGR is 1-methylcyclopropene (1-MCP), which is often used in the form of a complex with a molecular encapsulating agent as the most convenient way of storing, transporting and delivering 1-MCP to a target plant or to the ground. The contact between such with Petition 870180014706, of 23/02/2018, p. 5/52
    2/39 plexuses of 1-MCP and water will rapidly release 1-MCP gas from the complex in order to achieve PGR delivery to the target.
    [005] A challenge arises when a user of a concentrated formulation containing a 1-MCP complex wishes to dilute the formulation in water (for example, in a spray tank) in order to form an aqueous spray composition. Such aqueous spray agrochemical compositions are widely used in agriculture, but in the case of 1-MCP complexes their performance can sometimes be limited by the tendency of the 1-MCP complex to degrade in a spray tank upon contact with water . This can result in reduced efficiency and an unacceptable accumulation of 1-MCP gas in the free space of the spray tank.
    [006] Furthermore, due to the relatively complex supply chain of crop protection agents, such concentrated 1MCP complexes can be stored for long periods of time and subject to extreme variations in temperature, high shear, repeated vibration patterns and humidity during storage and transportation. Such supply chain conditions can increase the risk of formulation failures due to, for example, water-mediated degradation and stability problems.
    [007] Taking into account the various special conditions and situations in which concentrated 1-MCP complexes are stored, transported and used worldwide, there is a need for concentrated 1-MCP formulations that provide stability benefits in at least some these conditions and situations. There is still a need for such concentrated formulations with high loading, which are stable over a period of time when they are diluted with water in a wide variety of field conditions, and so that an end user can control the release rate of 1- MCP at the application site from a formulaPetition 870180014706, of 02/23/2018, p. 6/52
    3/39 concentrated or diluted spray.
    SUMMARY OF THE INVENTION [008] Liquid and stabilized cyclopropene compositions are provided that comprise fluid non-aqueous concentrated dispersions comprising a) a liquid non-aqueous continuous phase substantially immiscible in water and b) a dispersed solid phase comprising polymeric particles prepared from a polymeric particle polymerizable or curable resin, in which the outer surfaces of the polymeric particles comprise a solid colloidal material and in which the polymeric particles have at least one solid complex of a cyclopropene gas and a molecular encapsulating agent distributed in the dispersed phase. In one embodiment, the colloidal solid material is present in the dispersed solid phase in an amount effective to stabilize the resin in an emulsion state during the process used to prepare the dispersed phase. In another embodiment, the polymeric particles also contain a mobile non-crosslinkable chemical so that the extraction of that chemical from the dispersed solid phase makes it porous to allow the cyclopropene complex or gas to diffuse from the dispersed phase at a controlled rate. In another embodiment, the polymeric particles also contain a non-porous particulate mineral as a barrier to diffusion. The cyclopropene compositions of the invention can be used directly or diluted as plant growth regulators.
    [009] According to the invention, it has been observed that concentrated non-aqueous dispersions of solid complexes of a cyclopropene gas and a molecular encapsulating agent in a non-aqueous liquid and substantially immiscible in water can be prepared using polymerizable or curable resin polymers to trap the cyclopropene complex in a polymeric matrix in which a colloidal solid is used to stabilize the polymeric resin in a state
    Petition 870180014706, of 02/23/2018, p. 7/52
    4/39 of emulsion during the process used to prepare the dispersed phase. The cyclopropene complex can be distributed in the polymeric matrix of polymerizable or curable resin, which is dispersed as particles in the water-immiscible liquid continuous phase. Other active ingredients can be optionally dispersed, dissolved or suspended in the continuous phase. The release rate of cyclopropene from the dispersed solid phase can be controlled by the optional incorporation of non-crosslinkable mobile molecules into the dispersed phase, and these molecules are selected to be miscible with the unpolymerized or uncured resin that will form the soluble, particulate polymer matrix. in water or other medium with which the solid polymeric particles will come in contact, and of molecular dimensions that allow the gaps created in the dispersed phase when extracted to allow the desired release of the cyclopropene. The concentrated non-aqueous dispersions of the invention have an advantageously long period of protection from encapsulated cyclopropene gas providing practical utility in terms of storage, transport and use. The concentrated dispersions of the invention also provide the ability to control the rate of release of cyclopropene gas at the target site from the concentrate or a final diluted formulation.
    [0010] Polymerizable resins suitable for use in the preparation of the polymer matrix of the dispersed phase can be selected from monomers, oligomers or prepolymers that are curable or polymerizable to form thermoplastic or thermoset polymers.
    [0011] The present invention further relates to polymeric particles comprising a solid complex trapped by a cyclopropene gas and a molecular encapsulating agent, which is homogeneously or heterogeneously distributed within such polymeric particles or present as domains within such particles, and being
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    5/39 that the outer surface regions of the particles comprise a solid colloidal material.
    [0012] The polymerizable or curable resins used to prepare the polymeric matrix can be selected to be sufficiently hydrophobic so that when the concentrate is diluted in water to form an aqueous spray solution, the polymeric resin particles of the polymerized or cured resin protect the cyclopropene complex distributed in them from contact with water for a period of time that depends mainly on the size of the dispersed polymer particle and the polarity and porosity of the polymer matrix. In one embodiment, the cyclopropene complex is homogeneously distributed in the polymeric matrix or is present as domains within the polymeric matrix or particles thereof. One skilled in the art will quickly determine the optimum particle size of the solid phase within the scope of the present invention, which will be sufficient for the desired final application. A person skilled in the art will also quickly determine the optimal porosity of the polymeric matrix, for example, by selecting polymerizable or crosslinkable monomers that form an appropriate polymer matrix with an appropriate crosslinking density and crystallinity, by incorporating non-crosslinkable mobile molecules into the matrix. , which dissolve and diffuse from the matrix, and / or through the incorporation of a non-porous particulate mineral within the matrix as a barrier to diffusion. Those skilled in the art will also be able to select appropriate monomers, oligomers or prepolymers, which are polymerizable to form a thermoplastic or thermoset polymeric matrix with an appropriate composition of hydrophilic and hydrophobic chemical groups to optimize the polarity of the polymeric matrix.
    [0013] The present invention also includes a method for regulating
    Petition 870180014706, of 02/23/2018, p. 9/52
    6/39 the growth of plants in a location, such as soil or foliage, which comprises treating that location with a concentrated dispersion according to the invention or dispersing a concentrate according to the present invention in water and treating that location with the aqueous formulation final diluted obtained.
    DETAILED DESCRIPTION OF THE INVENTION [0014] Thus, in one embodiment, the concentrated liquid and non-aqueous dispersion compositions of the present invention comprise:
    a liquid continuous, non-aqueous and substantially immiscible water phase, optionally comprising at least one agrochemical active ingredient; and a dispersed solid phase, comprising polymeric particles prepared from a polymerizable or curable thermoplastic or thermoset resin, wherein the outer surfaces of the polymeric particles comprise a colloidal solid material in an amount effective to stabilize the resin in an emulsion state during the process used to prepare the dispersed phase and in which the polymeric particles have at least one solid complex of a cyclopropene gas and a molecular encapsulating agent distributed therein.
    [0015] It is understood that polymerizable or curable thermosetting resins suitable for use in the dispersed solid phase include all molecules that can be irreversibly polymerized or cured to form a polymeric matrix that will not melt or deform at elevated temperatures below the point of decomposition thermal. The polymerization reaction can be initiated thermally, by adding chemical curing agents or by appropriate irradiation to create radicals or ions, such as visible, UV, microwave or other electromagnetic radiation, or electron beam irradiation. Example 870180014706, of 02/23/2018, p. 10/52
    7/39 plos include phenolic resins, ureas, melamines, epoxies, polyesters, silicones, rubbers, polyisocyanates, polyamines and polyurethanes. In addition, biodegradable or biodegradable thermosetting resins can be detached including polyester or epoxy resins derived from natural materials such as vegetable oil, soy, wood and the like.
    [0016] In one embodiment, the concentrated dispersions for use in the liquid agrochemical compositions of the present invention are those formed using curing agents, monomers, oligomers, prepolymers or mixtures thereof that exhibit a slow cure or slow polymerization reaction when combined with curing agents under ambient conditions. Curing agents, monomers, oligomers, prepolymers or mixtures thereof which do not exhibit any significant increase in viscosity under ambient conditions are particularly suitable for a period of time of at least 15 minutes, more particularly 30 minutes, even more particularly 1 hour , after mixing with the curing agent.
    [0017] Polymerizable resins suitable for use in the invention can also be selected to be sufficiently hydrophobic so that when the concentrate is diluted in water to form an aqueous spray solution, the cured polymer matrix particles protect the complex from cyclopropene distributed in contact with water over a period of time that depends mainly on the size of the dispersed polymeric particle and the polarity and porosity of the polymeric matrix.
    [0018] Those skilled in the art will quickly determine the optimal particle size in the case of cured polymeric particles used within the scope of the present invention, which will be sufficient for the desired final application. In one embodiment, the polymeric particles of the dispersed solid phase b) have an average particle size of 1 to 200 microns, more particularly 1 to 100 micronsPetition 870180014706, of 02/23/2018, pg. 11/52
    8/39 crons and even more particularly, from 2 to 80 microns. In the context of the present invention, the average particle size means the diameter of the volumetric median, commonly referred to as D (v, 0.5).
    [0019] In one embodiment, suitable polymerizable resins are those that are substantially immiscible with the non-aqueous liquid used in the continuous phase.
    [0020] In one embodiment, the appropriate cyclopropenes are gaseous at room temperature and are selected from a compound of formula I:
    (R (I) [0021] Where n is a number from 1 to 4, n is suitably a number from 1 to 2, and n is more appropriately 1. The variable group R is selected from hydrogen, saturated C1 to C4 alkyl or unsaturated, hydroxy, halogen, alkoxy, amino and carboxy. In one embodiment, R is methyl.
    [0022] In one embodiment, the cyclopropene gas is selected from cyclopropene, dimethylcyclopropene and 1-methylcyclopropene (1-MCP).
    [0023] In one embodiment, the molecular encapsulating agents appropriate for the gas-cyclopropene PGRs include cyclodextrins, crown ethers, polyoxyalkylenes, porphyrins, polysiloxanes, phosphazenes, cucurbiturils and zeolites. In another embodiment, an appropriate molecular encapsulating agent is α-cyclodextrin.
    [0024] The solid complex of the cyclopropene gas and a molecular encapsulating agent is here sometimes called the cyclopropene complex.
    [0025] For example, in a method of preparing a cyclopropene complex, in which 1-MCP is encapsulated in a molecular encapsulating agent, 1-MCP gas is bubbled through a solution of α-cyclodextrin in water, from of which the complex first
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    9/39 precipitates and is then isolated by filtration. The cyclopropene complexes prepared by the above method are isolated, dried and stored in solid form, for example, as a powder containing active ingredient, for future addition to the concentrated dispersions of the invention.
    [0026] As highlighted above, in one embodiment, the cyclopropene complex is homogeneously distributed in the particles of the network or polymeric matrix that is formed due to the curing or polymerization of prepolymers, oligomers, thermoset or thermoplastic monomers and / or hardeners. Alternatively, the cyclopropene complex is present in such particles as domains within such a polymeric network or matrix. In one embodiment, the domains are open cells within the polymeric matrix. In another embodiment, the domains are closed cells within the polymeric matrix. [0027] In one embodiment, non-aqueous liquids suitable for use in the continuous phase a) are substantially immiscible in water and the affinity between the liquid and the cyclopropene complex distributed in the dispersed solid phase should be such as to allow substantially the entire complex cyclopropene remains in the dispersed solid phase and that substantially no cyclopropene complex migrates to the continuous phase. Those skilled in the art will be able to quickly determine whether a particular water-immiscible liquid meets this criterion for the cyclopropene complex in question using any standard test procedure to determine the partition coefficient of a material (in this case the cyclopropene complex) between the continuous liquid phase and the dispersed solid phase. Thus, in one embodiment, the dispersed solid phase b) is immiscible with the continuous phase a).
    [0028] Examples of water-immiscible non-aqueous liquids suitable for use in the continuous phase a) include: petroleum distillates, vegetable oils, silicone oils, methylated vegetable oils, hydroPetition 870180014706, from 02/23/2018, p. 13/52
    10/39 refined paraffin carbides (such as, for example, ISOPAR V), mineral oils, alkyl amides, alkyl lactates, alkyl acetates, or other liquids and solvents with a P log of 3 or more, and mixtures thereof. In one embodiment, the water-immiscible non-aqueous liquid used in the continuous phase a) has a log P of about 4 or more.
    [0029] In another embodiment, non-aqueous liquids suitable for use in the continuous phase a) are substantially immiscible with water. In the context of the invention, the term substantially immiscible in water means a non-aqueous liquid that forms two phases when mixed with water in a concentration of less than 10% by weight. [0030] In an embodiment of the invention, the dispersed solid phase b) comprises a polymer of thermoplastic resin or thermoset polymerized or cured with sufficient hydrophobicity so that when the concentrate is emulsified when diluted with water, the particles of such polymeric matrix continue to protect the cyclopropene complex from contact with water in the diluted aqueous spray formulation for a period of time within the acceptable range for such dilutions that will be used for agricultural spray applications. For example, in one embodiment, a significant amount of a cyclopropene complex can be protected from contact with water for more than about 1 hour in an agitated spray tank.
    [0031] In one embodiment, when the concentrate is diluted with water, some cyclopropene diffuses slowly from the polymeric particles. The release rate of cyclopropene from the diluted aqueous spray formulation in the spray tank can be adjusted, for example, by varying the size of the polymer particles dispersed in the concentrate, the concentration of the cyclopropene complex in the polymer particles, the pH of the dispersion in the spraying, the optional inclusion of a non-crosslinkable mobile chemical in the
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    11/39 polymeric particles, the optional inclusion of non-porous particulate minerals as a barrier for diffusion within the polymeric particles, and the amount and type of polymerizable or curable thermoplastic or thermoset resin, including monomers, oligomers, prepolymers and hardeners used to form the polymeric particles.
    [0032] The release rate of cyclopropene from the dispersed solid phase can also be controlled by the optional incorporation into the dispersed phase of non-porous particulate minerals as a barrier to diffusion. For the purposes of the present invention, non-porous means that the mineral has no larger pores than the individual cyclopropene molecules, so that the diffusion coefficient of cyclopropene through the mineral particles is less than 10 -15 m 2 / s.
    [0033] In this regard, the dispersed phase may also include one or more non-crosslinkable mobile chemicals so that the extraction of that chemical from the dispersed phase makes it porous to allow the cyclopropene active ingredient to diffuse from the dispersed phase . Examples include acids, bases, surfactants, polymers, copolymers, substantially water-soluble compounds or substantially water-immiscible compounds.
    [0034] The mobile non-crosslinkable chemical in the dispersed phase can optionally be selected to also function as a surfactant or dispersant within the concentrated liquid dispersion used to prepare the final liquid agrochemical compositions of the present invention. If selected in this way, the mobile chemical will adsorb to the surfaces of the polymeric particles present in the concentrated dispersion and thus stabilize the dispersion of these polymeric particles. This behavior can be observed in at least one of the following ways: the polymeric particles will be individually distributed and not in the form of agglomerates denPetição 870180014706, of 02/23/2018, p. 15/52
    12/39 of the concentrated dispersion when viewed microscopically, the viscosity of the concentrated dispersion will be reduced when the mobile chemical is added, or the polymeric particles will have a greater tendency to remain within the dispersed phase than will be lost to the continuous phase when the final liquid agrochemical compositions are prepared. Examples of suitable and useful water-insoluble polymers for this purpose include copolymers of an α-olefin and an N-vinylpyrrolidone such as, for example, alkylated vinylpyrrolidone copolymers such as Agrimers (eg Agrimer® AL-22, based on 1- ethylenehexadecyl-2-pyrrolidinone) (International Specialty Products (ISP) Corporation), or copolymers of an αolefin and ethylene glycol such as, for example, Atlox 4914 from Croda Corp. [0035] In one embodiment, the concentrated liquid and non-aqueous dispersion compositions of the present invention comprise the solid phase in the form of finely divided and suspended cyclopropene / polymer complex particles, which comprise a solid colloidal material on the surface thereof and containing at least least one cyclopropene complex, where the average particle diameter of such polymeric particles is generally less than 200 microns, often less than 100 microns, for example, in the range of 1 to 200, particularly in the range of 1 to 100 and especially in the range from 2 to 80 microns.
    [0036] In one embodiment, the solid colloidal material is a Pickering colloidal emulsion stabilizer.
    [0037] In the context of the present invention, a solid colloidal material is a material whose properties of interest are determined by the interactions of its surfaces with other materials. Colloidal solids are therefore necessarily those with a high specific surface area, typically greater than 10 m 2 / g. Colloidal solids are capable, for example, of stabilizing liquid emulsions. Petition 870180014706, of 23/02/2018, p. 16/52
    13/39 of immiscibles, as described, for example, in WO 2008/030749. When used for this purpose, such colloidal solids may be called Pickering colloids, colloidal emulsion stabilizers or other equivalent terms. Functional tests are known to know whether a colloidal solid can stabilize a resin in an emulsion state during the curing reaction as used herein. Such a test is described below in paragraph 97. Not all colloidal solids are able to stabilize any pair of immiscible liquids, and a functional test of the type can be used by those skilled in the art to identify an appropriate colloid.
    [0038] As mentioned above, the release rate of cyclopropene from the dispersed solid phase can also be controlled by the optional incorporation into the dispersed phase of non-porous particulate minerals as a barrier to diffusion. In some circumstances, the same non-porous particulate mineral used as a barrier for diffusion in the dispersed phase can also serve as the colloidal emulsion stabilizer. In that case, the particulate mineral can be added at two separate points during the preparation process as described below - firstly to the dispersed phase concentrate to be incorporated into the dispersed phase particles, and secondly to the continuous phase to stabilize the resin in an emulsion state during the polymerization or curing reaction. [0039] In some cases, the spontaneity and stability of the polymer particles of the dispersed phase b) against flocculation when diluted in water, can be improved by adding one or more emulsifiers to the continuous phase of non-aqueous solvent and immiscible in water of the concentrated dispersion . Examples of suitable emulsifiers that serve this purpose include: ethoxylated tristyrylphenol phosphate esters (such as Rhodia's Soprophor 3D33), polyalcoxylated alcohols such as Rhodia's BC-610 Rhodasurf or polyalkoxy sorbitan monooleate Petition 870180014706, from 23/02/2018, page. 17/52
    14/39 side (4 moles of OE) (Tween 21 from Croda).
    [0040] In another embodiment, the general properties of physical stability, fluidity and manipulation of the concentrated dispersion can be improved by adding one or more surfactants or dispersants to the continuous phase of a non-aqueous and water-immiscible solvent, including polyvinylpyrrolidone (Agrimer 90 from ISP) , vinyl ester polymer of acetic acid with 1-ethylene-2-pyrrolidone (Agrimer VA 5I from ISP), and non-ionic surfactants. Suitable non-ionic surfactants are, for example, those that are hydrophilic with an HLB (acronym for hydrophilic-lipophilic balance) greater than about 12, such as Croda's Atplus MBA 13/30, amine-based block copolymers such as Tertronic 1107 from BASF, or polyalkoxylated butanol (Toximul 8320 from Stepan).
    [0041] As used in this document, the term degradation in reference to the cyclopropene complex denotes the release of the active ingredient of cyclopropene, that is, the water-soluble, water-dispersible or water-sensitive agrochemical of the molecular encapsulating agent, as well as the degradation of the agrochemical, as a result of contact with water. Degradation can be determined simply by measuring the amount of cyclopropene present before and after contact with water.
    [0042] The term agrochemically active ingredient associated with optional use in the continuous phase a) refers to chemicals and biological compositions, such as those described here, that are effective in killing, preventing or controlling the growth of unwanted pests, such as plants, insects, mice, microorganisms, algae, fungi, bacteria, and the like (as pesticide active ingredients). The term can also be assigned to compounds that control plant growth in a desired manner (for example, plant growth regulators), to a compound that mimics the systemic responsePetition 870180014706, of 23/02/2018, p. 18/52
    15/39 ca activated of natural resistance observed in plant species (for example, a plant activator) or to a compound that reduces the phytotoxic response to a herbicide (for example, a protector). If more than one is present, the agrochemically active ingredients are independently present in an amount that is biologically effective when the composition is diluted, when necessary, in an appropriate volume of a liquid vehicle, for example, water, and applied to the targeted target, for example, in the foliage of a plant, at the location of the plant or to the soil where the cultivation of such plants is intended. [0043] Examples of optional agrochemical active ingredients suitable for use in the continuous phase a) according to the present invention include, but are not limited to: fungicides such as azoxystrobin, chlorotalonil, cyprodinil, diphenoconazole, fludioxonil, mandipropamide, picoxystrobin, propiconazole, pyraclostrobin, tebuconazole , thiabendazole and trifloxystrobin; herbicides such as acetochlor, alachlor, ametrine, anilofos, atrazine, azafenidin, benfluralin, benfuresate, bensulide, benzfendizone, benzofenap, bromobutide, bromophenoxim, bromoxynil, butachlor, butafenacil, butamiphos, chloramide, butralid, carbamide, butralin dimethyl, chlortiamide, cinidon-ethyl, cinmetiline, clomazone, clomeprop, cloransulam-methyl, cyanazine, cyclate, desmedifam, desmetrina, diclobenil, diflufenican, dimepiperate, dimetachlor, dimetamethrin, dimetenamide, dinoteramide, dinoteramide, dinetheramide, dinoteramide, dinoteramide, dinenzamide, dinoteramide, dinenzamide EPTC, sprocarb, etalfluralin, etofumesate, etobenzanide, phenoxaprop-ethyl, phenoxaprop-P-ethyl, fentrazamide, flamprop-methyl, flamprop-M-isopropyl, fluazolate, flucloraline, flufenacet, flumiclorac-pentyl, flumoxorol, flumoxorol, flumoxorin fluridone, flurtamone, flutiacet-methyl, indanofan, isoxaben, isoxaflutole, lenacil, linuron, mefenacet, mesotrione, metamitron, metazachlor, metabenztiazuron, methyldimron, metobenzuron, metolachlor, metosulam, methoxyuron, metribuzin, molinate, naproanilide, napropamide,
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    16/39 neburon, norflurazon, orbencarb, orizaline, oxadiargil, oxadiazone, oxifluorfen, pebulate, pendimethalin, pentanochlor, petoxamide, pentoxazone, fenmedipam, pinoxaden, piperofos, pretilachlor, propyl, propyl, propamine, propamine, propyl, propluent, propylamine , propisochlor, propizamide, prosulfocarb, piraflufen-ethyl, pyrazogyl, pyrazolinate, pyrazoxifen, pyributicarb, pyridate, pyriminobac-methyl, quinclorac, siduron, simazine, simetrin, S-metolachlor, sulcotrione, sulfentrazone, tebutazone, tebutazone, tebutazone, tebutazone, tebutazone , terbutrin, tenilchlor, thiazopyr, thidiazimine, thiobencarb, thiocarbazil, trialate, trietazine, trifluralin and vernolate; herbicidal protectors such as benoxacor, diclormid, fenclorazol-ethyl, fenclorim, flurazol, fluxofenim, furilazol, isoxadifenetil, mefenpir; alkali metal, alkaline earth metal, ammonium cation or mefenpir sulfonium; mefenpir-diethyl and oxabetrinil; insecticides such as abamectin, clothianidin, emamectin benzoate, gamma cyhalothrin, imidacloprid, lambda cyhalothrin, permethrin, resmethrin and thiamethoxam. [0044] In one embodiment, the active ingredients in the continuous phase a) can be in the form of a solution, an emulsion, a microemulsion, a microcapsule, a particle and / or a fine particle that is rapidly suspended in the liquid. In the context of the present invention, a fine particle is a particle substantially smaller than the dimensions of the solid polymer particles of the dispersed phase, so that a plurality (at least 10) particles of active ingredient are within each particle of the dispersed phase, while a non-fine particle is a particle slightly smaller than the dimensions of the solid polymer particles in the dispersed phase, so that each polymer particle contains only a few particles of active ingredient.
    [0045] Other aspects of the invention include a method to prevent or combat an infestation of a species of plants by pests, and to regulate the growth of plants by diluting an amount of the
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    17/39 concentrated liquid and non-aqueous dispersion composition in an appropriate liquid carrier, such as water or liquid fertilizer, and apply the diluted formulation to the plant, tree, animal or location as desired. The concentrated formulations of the present invention can also be combined in a continuous flow apparatus with water in spray application equipment, so that no holding tank is necessary for the diluted product.
    [0046] Concentrated liquid and non-aqueous dispersion compositions can be conveniently stored in a container from which they are poured, or pumped, or into which a liquid vehicle is added prior to application.
    [0047] The advantages of the concentrated liquid and non-aqueous dispersion compositions of the present invention include: stability in storage for prolonged periods, for example, 6 months or more at room temperature; simple manipulation for users is possible because the dilution is made with water, or another liquid vehicle, for the preparation of the application mixes; reduced degradation of the cyclopropene complex; reduced settling of the suspension during storage or when it is diluted; the compositions can be easily resuspended or redispersed with just a little stirring.
    [0048] The rate of application of the composition of the invention will depend on several factors including, for example, whether any optional agrochemical active ingredients have been selected for use, the type of pest to be controlled or the plants whose growth will be regulated and the formulations selected for use. use, and whether the compost will be applied to foliage, soil or to be absorbed by the roots or by chemigation. However, as a general guide, an application rate of 1 to 2000 g of active ingredient per hectare is appropriate, in particular 2 to 500 g of active ingredient per hectare. In the case of 1-MCP and regulation 870180014706, of 02/23/2018, p. 21/52
    18/39 plant growth rates, utilization rates are about 0.1 to 50 g per hectare.
    [0049] In one embodiment, the appropriate rates for the optional agrochemically active ingredients used in the inventive compositions are comparable to the rates described on current product labels containing such active ingredients. For example, Quadris® brand azoxystrobin can be applied at a rate of 112 g to 224 g ai / hectare and the Quilt ™ brand azoxystrobin (75 g / L) / propiconazole (125 g / L) premix can be applied. applied at a rate of 0.75 to 1.5 L / ha.
    [0050] In one embodiment of the present invention, the concentrated dispersion composition comprises a cyclopropene complex and that cyclopropene complex is distributed within a polymer particle that is dispersed in a liquid continuous phase substantially immiscible in water, thus forming a concentrated oily dispersion. of a solid in oil.
    [0051] As used herein, the term agrochemically effective amount means the amount of an agrochemically active compound that controls or adversely modifies target pests or that regulates plant growth (PGR). For example, in the case of herbicides, an effective amount as a herbicide is the amount of herbicide that is sufficient to control or modify plant growth. Control or modification effects include all deviations from natural development, for example, killing, retarding, burning leaves, albinism, dwarfism and the like. The term plants refers to all the physical parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stems, foliage and fruits. In the case of fungicides, the term fungicide will mean a material that kills or materially inhibits the growth, proliferation, division, reproduction or spread of fungi. As used
    Petition 870180014706, of 02/23/2018, p. 22/52
    19/39 in this document, the term amount effective as a fungicide or amount effective to control or reduce fungi in reference to the fungicidal compound is the amount that will kill or materially inhibit the growth, proliferation, division, reproduction or spread of a significant number of fungi . As used herein, the terms insecticide, nematicide or acaricide will mean a material that kills or materially inhibits the growth, proliferation, reproduction or spread of insects, nematodes or mites, respectively. An effective amount of the insecticide, nematicide or acaricide is an amount that will kill or materially inhibit the growth, proliferation, reproduction or spread of a significant number of insects, nematodes or mites.
    [0052] In one aspect, as used herein, regulating (plant) growth, plant growth regulator, PGR, or regulating provided by a PGR present in the concentrated dispersion includes the following plant responses; inhibition of cell elongation, for example, reduction of the height of the stems and internode distance, reinforcement of the wall of the stems, thus increasing the resistance to lodging; compact growth in ornamental plants for the economical production of plants of improved quality; production of better fruits; increase in the number of ovaries to increase yield; induction of senescence in the formation of tissues allowing the fruits to separate from the plant; defoliation of ornamental trees and shrubs or nurseries for mail order sales in winter; defoliation of trees to interrupt chains of parasitic infection; acceleration of ripening, aiming to schedule the harvest by reducing the harvest to one or two harvests and interrupting the food chain of harmful insects.
    [0053] The cyclopropene gases present in the concentrated dispersion 870180014706, of 02/23/2018, p. 23/52
    20/39 trades are PGRs that act as inhibitors of ethylene binding. Such a well-known cyclopropene gas is 1-methylcyclopropene (MCP). 1-MCP prevents the ethylene signal from initiating stress responses in plants, which inhibits the sensitivity of plants or parts of plants (for example, fruits and flowers) to ethylene by inhibiting its perception. Consequently, in another aspect, regulating growth, regulating (plant) growth, plant growth regulator, PGR, regulating or regulating also include the use of a water dispersible concentrated dispersion composition defined in accordance with the present invention for increase yield and / or improve the vigor of an agricultural plant. In accordance with an embodiment of the present invention, inventive compositions are used to improve tolerance to biotic stress factors such as fungi, bacteria, viruses and / or insects and abiotic stress factors such as heat stress, stress due to lack of nutrients , cold stress, drought stress, UV stress and / or salt stress from an agricultural plant.
    [0054] The selection of application rates related to providing a desired level of pesticidal activity and / or regulating plant growth for a composition of the invention is routine for those skilled in the art to optimize the bio-performance of the active ingredient in question . Application rates will depend on factors such as the degree of pest pressure, plant conditions, conditions related to climate and cultivation, as well as the activity of the agrochemically active ingredients and any applicable restrictions on the label relating to the rate.
    [0055] The invention also relates to liquid agrochemical compositions comprising
    a) a liquid continuous phase, non-aqueous and substantially immiscible with water, optionally comprising at least
    Petition 870180014706, of 02/23/2018, p. 24/52
    21/39 an agrochemically active ingredient (for example, in a selected form of a solution or dispersion such as an emulsion, a microemulsion or a suspension of microcapsules or fine particles); and
    b) a dispersed solid phase, comprising polymeric particles prepared from a polymerizable or curable thermoplastic or thermoset resin, in which the outer surfaces of the polymeric particles comprise a colloidal solid material in an amount effective to stabilize the resin in an emulsion state during curing or polymerization reaction and in which the polymeric particles have at least one cyclopropene complex distributed in them.
    [0056] Another aspect of the invention relates to a diluted aqueous spray composition to regulate plant growth in a location comprising
    a) a continuous aqueous phase comprising an appropriate liquid carrier, such as water or liquid fertilizer, in an amount sufficient to obtain the desired final concentration of the active agrochemical ingredients in the spray composition;
    b) a dispersed solid phase, comprising polymeric particles prepared from a polymerizable or curable thermoplastic or thermoset resin, wherein the outer surfaces of the particles comprise a colloidal solid material in an amount effective to stabilize the resin in an emulsion state during curing or polymerizing reaction and in which the polymeric particles have at least one cyclopropene complex distributed in them; and
    c) optionally at least one agrochemically active ingredient dispersed, dissolved, suspended, microemulsified or emulsified in the liquid carrier.
    Petition 870180014706, of 02/23/2018, p. 25/52
    22/39 [0057] In another embodiment, the invention refers to a diluted composition for a very low volume application (ULV; ultra low volume), which comprises:
    a) a continuous phase, comprising a carrier solvent which has a flash point above 55 ° C, in an amount sufficient to obtain the desired final concentration of each of the agrochemically active ingredients in the ULV composition;
    b) a dispersed solid phase, comprising polymeric particles prepared from a polymerizable or curable thermoplastic or thermoset resin, wherein the outer surfaces of the particles comprise a colloidal solid material in an amount effective to stabilize the resin in an emulsion state during curing or polymerization reaction and in which the particles have at least one cyclopropene complex distributed in them.
    [0058] The invention also refers to a method to combat or prevent pests in crops of useful plants or to regulate the growth of such crops, wherein said method comprises:
    [0059] treating the desired area, such as plants, parts of plants or the location thereof with a concentrated composition comprising:
    a) a liquid continuous phase, non-aqueous and substantially immiscible with water, optionally comprising at least one agrochemically active ingredient;
    b) a dispersed solid phase, comprising polymeric particles prepared from a polymerizable or curable thermoplastic or thermoset resin, wherein the outer surfaces of the particles comprise a colloidal solid material in an amount effective to stabilize the resin in an emulsion state during curing or polymerization reaction and in which the particles have at least one cyclopropene complex distributed in them; and
    Petition 870180014706, of 02/23/2018, p. 26/52
    23/39 dilute the concentrated composition, when necessary, in an appropriate vehicle, such as water, aqueous liquid fertilizer or a vehicle solvent with a flash point above 55 ° C, in an amount sufficient to obtain the desired final concentration of each agro-chemically active ingredients; and then treat the desired area, such as plants, parts of plants, or their location with the diluted spray or ULV composition.
    [0060] The term plants refers to all the physical parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stems, buds, flowers, foliage and fruits. The term local refers to the place where the plant is growing or will be grown.
    [0061] The composition according to the invention is suitable for all application methods conventionally used in agriculture, for example, pre-emergence application, post-emergence application and seed treatment. The compositions according to the invention are suitable for pre- or post-emergence applications in growing areas.
    [0062] The compositions according to the invention are especially suitable to combat and / or prevent pests in useful plant cultures or to regulate the growth of such plants. Preferred useful plant crops include canola, cereals such as barley, oats, rye and wheat, cotton, corn, soybeans, sugar beets, fruits, berries, nuts, legumes and vegetables, flowers, trees, shrubs and grass. The components used in the composition of the invention can be applied in various ways known to those skilled in the art, in various concentrations. The rate at which the compositions are applied will depend on the particular types of pests to be controlled, the degree of control required, and the time and method of application.
    [0063] It should be understood that cultures also include those
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    24/39 cultures that have been made tolerant to herbicides or classes of herbicides (for example, ALS, GS, EPSPS, PPO, ACCase and HPPD inhibitors) by conventional breeding methods or by genetic engineering. An example of a crop that has been made tolerant to imidazolinones, for example, imazamox, by conventional breeding methods is Clearfield® summer rapeseed (canola). Examples of crops that have been made tolerant to herbicides by means of genetic engineering methods include, for example, glyphosate and glufosinate resistant maize varieties available on the market under the trademarks RoundupReady® and LibertyLink®.
    [0064] It should also be understood that crops are those that have been made resistant to harmful insects by means of genetic engineering methods, for example, Bt maize (resistant to the European corn borer), Bt cotton (resistant to the cotton weevil) and also Bt potatoes (resistant to the Colorado potato beetle). Examples of Bt maize are NK® Bt 176 hybrids (Syngenta Seeds). Bt toxin is a protein that is naturally formed by bacteria from the soil Bacillus thuringiensis. Examples of toxins, or transgenic plants capable of synthesizing such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that encode an insecticidal resistance and express one or more toxins are KnockOut® (corn), Yield Gard® (corn), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Vegetable crops or their seed materials can be resistant to herbicides and, at the same time, resistant to insect feeding (stacked transgenic events). For example, seeds may have the ability to express an insecticidal Cry3 protein at the same time as
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    25/39 are tolerant to glyphosate.
    [0065] It should also be understood that cultures are those that are obtained by conventional breeding methods or genetic engineering and contain the so-called resulting characteristics (for example, improved storage stability, higher nutritional value and improved taste).
    [0066] Other useful plants include grass, for example, on golf courses, lawns, parks and on the side of roads or commercially grown for lawns, and ornamental plants such as flowers or shrubs.
    [0067] The cultivation areas are areas of land where the cultivated plants are already growing or where the seeds of these cultivated plants have been planted, and also areas of land where it is intended to cultivate such cultivated plants.
    [0068] Other active ingredients such as herbicide, plant growth regulator, algaecide, fungicide, bactericide, viricide, insecticide, rodenticide, acaricide, nematicide or molluscicide may be present in the emulsion formulations of the present invention or may be added as a partner of tank mix with emulsion formulations.
    [0069] The compositions of the invention can also comprise other inert additives. Such additives include thickeners, flow promoters, wetting agents, antifoaming agents, biocides, lubricants, fillers, displacement control agents, deposition promoters, adjuvants, evaporation retardants, cryoprotectants, aroma agents to attract insects, agents protection against UV, fragrances and the like. The thickener can be a compound that is soluble or capable of swelling in water, for example, xanthan polysaccharides (for example, anionic heteropolysaccharides such as RHODOPOL® 23 (xanta gumPetition 870180014706, from 23/02/2018, p. 29 / 52
    26/39 na) (Rhodia, Cranbury, NJ)), alginates, guar gums or celluloses; synthetic macromolecules, such as polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols, modified cellulose-based polymers, polycarboxylates, bentonites, montmorillonites, hectonites, or atapulgites. The cryoprotective agent can be, for example, ethylene glycol, propylene glycol, glycerol, diethylene glycol, sucrose, water-soluble salts such as sodium chloride, sorbitol, triethylene glycol, tetraethylene glycol, urea or mixtures thereof. Representative antifoaming agents are polydialkylsiloxanes, in particular polydimethylsiloxanes, fluoroaliphatic esters or perfluoroalkylphosphonic / perfluoroalkylphosphonic acids or their salts and mixtures. Polydimethylsiloxanes, such as Dow Corning® Antifoam A or Antifoam B. are preferred. Representative biocides include 1,2-benzisothiazolin-3-one, available as PROXEL® GXL (Arch Chemicals).
    [0070] The compositions of the invention can be mixed with fertilizers and still maintain their stability. Fertilizers can comprise, for example, sulfur, nitrogen, phosphorus and / or potassium. [0071] The compositions of the invention can be used in conventional methods of agriculture. For example, the compositions of the invention can be mixed with water and / or fertilizers and can be applied pre-emergence and / or post-emergence in a desired location by any means, such as aircraft spray tanks, direct injection spray equipment. , back spray tanks, cattle immersion tanks, agricultural equipment used in soil spraying (eg boom sprayers, hand sprayers) and the like. The desired location can be soil, plants and the like.
    [0072] In one embodiment, the concentrated dispersion is prepared by:
    dissolution or suspension of the cyclopropene complex
    Petition 870180014706, of 02/23/2018, p. 30/52
    27/39 in a liquid, curable and non-aqueous mixture, comprising at least one appropriate polymerizable or curable thermoplastic or thermoset resin (comprising monomers, oligomers, prepolymers or mixtures thereof), optionally an appropriate hardener, catalyst or initiator, and an or more optional components selected from non-porous particulate minerals as a diffusion barrier and / or non-crosslinkable mobile chemicals;
    emulsification of said solution or suspension in a non-aqueous liquid immiscible with water to an average droplet size of 1 to 200 microns, the liquid also containing a colloidal solid as an emulsion stabilizer (from Pickering) and, optionally, a certain hardener, appropriate catalyst or initiator capable of diffusing into dispersed uncured resin droplets; and effecting the crosslinking, polymerization or curing of the polymerizable or curable thermoplastic or thermoset resin mixture to produce polymeric particles containing at least one cyclopropene complex distributed in them and colloidal solids on their surfaces in an amount effective to stabilize the resin in a state of emulsion during the curing or polymerization reaction and that after curing / polymerization are dispersed in the non-aqueous liquid.
    [0073] In one embodiment, the concentrated dispersion is prepared by adding a premixed dispersed phase to a premixed continuous phase, in which:
    1) the pre-mixture of the dispersed phase is prepared by mixing, with a high shear mixer: at least one cyclopropene complex, at least one monomer, oligomer, prepolymer or mixture of these suitable thermosetting resin, a hardener, catalyst or appropriate initiator, an optional non-cross-linkable mobile chemical and an optional non-porous particulate mineral as barPetition 870180014706, of 23/02/2018, pg. 31/52
    28/39 apply for diffusion;
    2) the premix of the continuous phase is prepared by mixing, with a low shear mixer: a non-aqueous liquid substantially immiscible in water with a colloidal solid as an emulsion stabilizer.
    [0074] Mixtures resulting from the dispersed phase premix and the continuous phase premix are stirred under high shear conditions for an appropriate period of time to form a Pickering emulsion and then heated or exposed to light or other conditions of electromagnetic radiation (UV, microwave), as needed, in order to polymerize the dispersed phase. The shear rate and duration of the emulsification can be quickly determined by a person skilled in the art, guided by the following observations: if the shear rate is very low, the emulsion and the resulting polymer matrix particles are relatively coarse and may be larger than that desired; if instead the shear rate is too high or lasts a long time, eventually the emulsion stabilizer colloid becomes so depleted from the continuous phase that any new interfacial surfaces between the dispersed and continuous phases are not actually protected, and at that moment a rapid coalescence or dispersed phase heterofloculation occurs and the Pickering emulsion is in fact lost.
    [0075] In one embodiment, the cyclopropene complex can be ground to the desired particle size prior to dispersion within the polymerizable resin (monomers, oligomers and / or prepolymers, etc.) that will form the polymeric matrix particles. The solid can be ground in a dry state using an air mill or other appropriate equipment, as needed, to obtain the desired particle size. The particle size can be an average particle size of about 0.2 to about 20 mPetition 870180014706, from 23/02/2018, pg. 32/52
    29/39 crons, suitably about 0.3 to about 15 microns, more suitably about 0.5 to about 10 microns.
    [0076] In one embodiment, the mixture of the dispersed phase premix and the continuous phase premix is stirred under high shear conditions for 5 to 10 minutes and heated to a temperature of about 30 to 120 ° C for about 0.1 to 10 hours in order to effect the curing reaction.
    [0077] Polymerizable resins suitable for use in the preparation of solid polymer particles from the dispersed solid phase include thermosetting resins such as epoxy resins, phenolic resins, polyurea resins, polyurethane resins, aminoplast resins and polyester resins.
    [0078] In one embodiment, the polymerizable resins suitable for use in the preparation of solid polymer particles from the dispersed solid phase are biodegradable or biodivivable including, for example, polyester or epoxy resins derived from natural materials such as vegetable oil, soy, wood and the like .
    [0079] In relation to epoxies, all the usual pre- polymers or monomers di- and polyepoxies, or mixtures thereof, are epoxy resins suitable for carrying out this invention. In one embodiment, the appropriate epoxy resins are those that are liquid at room temperature. Di- and poliepoxies can be aliphatic, cycloaliphatic or aromatic compounds. Typical examples of such compounds are diglycidyl ethers of bisphenol A, glycidyl ethers and βmethylglycidyl ethers of polyols or aliphatic or cycloaliphatic diools, including those of hydrogenated bisphenol A, ethylene glycol, 1,2-propanediol, 1,3propanediol, 1,4- butanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane or 1,4-dimethylolcyclohexane or 2,2-bis (4-hydroxycyclohexyl) propane, the glycidyl ethers of di- and polyphenols, typically residinhydroxy, 4,4'-resorcinol, 4,4 ' 4.4 'Petition 870180014706, of 02/23/2018, p. 33/52
    30/39 dihydroxydiphenyl-2,2-propane, novolac and 1,1,2,2-tetrakis (4hydroxyphenyl) ethane. Other examples are N-glycidyl compounds, including diglycidyl compounds of ethylene urea, 1,3-propylene urea or 5-dimethylidantoin or 4,4'-methylene-5,5'-tetramethyldihidantoin, or those such as triglycidyl isocyanurate.
    [0080] Other glycidyl compounds of technical importance are the glycidyl esters of carboxylic acids, especially di- and polycarboxylic acids. Typical examples are the glycidyl esters of succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, tetra and hexahydrophthalic acid, isophthalic acid or trimellitic or dimerized fatty acids.
    [0081] Exemplary polyepoxies that differ from glycidyl compounds are vinylcyclohexene and dicyclopentadiene, 3- (3 ', 4'-epoxycyclohexyl) -8,9-epoxy-2,4-dioxaspiro [5.5] undecane ester, the ester 3,4-epoxycyclohexanecarboxylic acid 3 ', 4'-epoxycyclohexylmethyl, butadiene diepoxide or isoprene diepoxide, epoxidated linoleic derivatives or epoxidated polybutadiene.
    [0082] Other suitable epoxy resins are diglycidyl ethers or advanced diglycidyl ethers of dihydric phenols or dihydric aliphatic alcohols of 2 to 4 carbon atoms, preferably diglycidyl ethers or advanced 2,2-bis (4-hydroxyphenyl) diglycidyl ethers propane and bis (4-hydroxyphenyl) methane or a mixture of these epoxy resins. Biodegradable or bioderivated epoxies such as diglycidyl ethers of vegetable oils are also suitable for use in the present invention.
    [0083] The appropriate epoxy resin hardeners for carrying out this invention can be any suitable epoxy resin hardener, typically selected from primary and secondary amines and their adducts, cyanamide, diciandiamide, polycarboxylic acids, polycarboxylic acid anhydrides, polyamines, polyamines. 870180014706, of 02/23/2018, p. 34/52
    31/39 amides, polyaducts of amines and polyepoxies and polyols.
    [0084] Other suitable hardeners are polycarboxylic acid anhydrides, typically phthalic anhydride, naic anhydride, methyl naic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and, in addition, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
    [0085] Phenolic resins comprise resole phenolic resins and novolac phenolic resins. Resole phenolic resins can be formed by the reaction between phenol or substituted phenols and an excess of formaldehyde in the presence of a basic catalyst. Novolac phenolic resins can be obtained by reacting between an excess of phenol or substituted phenols such as, for example, resorcinol, parasol substituted phenol such as p-tert-butyl phenol or cresol and formaldehyde in the presence of an acid catalyst.
    [0086] Polyester resins comprise a base resin and a catalyst. The base resin component of the system can include a reactive polymer, or a monomer, or a combination of the two. Suitable reactive polymers include, but are not limited to, unsaturated polyesters, vinyl esters, and hybrid systems of epoxy polyester and acrylate-polyester that polymerize through a free radical mechanism. Suitable monomers include, but are not limited to, styrene, vinyl toluene, other methyl styrene monomers, methyl methacrylate and other acrylate monomers. Suitable peroxide catalysts include, but are not limited to, ketone peroxides, cumila hydroperoxides, dibenzoyl peroxides, peroxyesters, peroxicetals and peroxydicarbonates. Suitable ketone peroxides include, but are not limited to, methyl ethyl ketone peroxide, 2,4-pentadione peroxide, methyl isobutyl ketone peroxide, acetyl acetone peroxide, cyclohexanone peroxide.
    [0087] Examples of appropriate aminoplast condensates
    Petition 870180014706, of 02/23/2018, p. 35/52
    32/39 include urea, diciandiamide, melamine or oxamide and aldehydes, such as formaldehyde, acetaldehyde, isobutyraldehyde, hydroxypivaldehyde, crotonaldehyde, hydroxyacetaldehyde, furfurol, hydroxymethylfurfurol, glyoxal and glucose. Among the appropriate aminoplastics can also be mentioned the condensation products of urea and formaldehyde, urea and glyoxal, urea and acetaldehyde, urea and isobutyraldehyde, urea and crotonaldehyde, urea and hydroxypivalaldehyde and 2-oxo-4-methyl-6-ureidohexahidropir.
    [0088] In the literature it has been taught that solids, such as silica and clays, can be used as viscosity modifiers in agrochemical formulations to inhibit gravity-induced sedimentation or the separation of a cream by forming a network or gel in the continuous phase , thus increasing the low shear viscosity and reducing the movement of small particles, surfactant micelles or emulsion droplets. Instead, the colloidal solids of the present invention serve as a processing aid by stabilizing the droplets containing the resin monomers during curing by adsorbing to the transient liquid-liquid interface, thus forming a barrier around the curing droplets so that the droplets of contact curing or neighbors are unable to coalesce, regardless of the curing droplets being accumulated in a sediment or layer of cream. It is possible to distinguish the two different functions - the rheological modification or the emulsion stabilization, through a functional test as described below. The effectiveness of the colloidal solid in stabilizing the curing polymeric droplet emulsions depends on the size of the particles, shape of the particles, concentration of the particles, wettability of the particles and interactions between the particles. The colloidal solids must be small enough so that they can coat the surfaces of dispersed curing liquid polymeric droplets, and the liquid droplets of
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    33/39 curing must be small enough for acceptable dispersion stability against sedimentation of the resulting solid polymeric particles if the concentrated dispersion containing such particles is diluted for use. The final polymeric particles (and therefore the colloidal solids) will also need to be small enough to provide an acceptably homogeneous distribution of the product at the target location. The colloidal solid must also have sufficient affinity with both liquids forming the dispersed and continuous phases so that they are able to adsorb to the transient liquid-liquid interface and thus stabilize the emulsion during curing. This wettability characteristic, the shape of the particles and the suitability for stabilizing the Pickering type emulsion can be quickly evaluated by preparing a control formulation that does not contain the colloidal solid as an emulsion stabilizer. In this case, the curing liquid polymeric droplets coalesce and form a consolidated mass instead of a dispersion of fine solid polymeric particles.
    [0089] In one embodiment, colloidal solids have a particle size diameter of the numerical median measured by electron scanning microscopy from 0.01 to 2.0 microns, particularly from 0.5 microns or less, more particularly from 0 , 1 micron or less.
    [0090] A wide variety of solid materials can be used as colloidal stabilizers to prepare the dispersions of the present invention including carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica and clays. The appropriate colloidal stabilizers are insoluble in any of the liquid phases present in the preparation of the concentrated formulation. If an agrochemical active ingredient has adequately low solubility in any liquid used to dilute competition 870180014706, of 23/02/2018, p. 37/52
    34/39 final position, and in the continuous and dispersed (transient) liquid phases, which is less than 100 ppm at room temperature, and can be prepared with an appropriate particle size, and have appropriate wetting properties for the liquid-interface transient liquid as described above, in which case it is also possible that this active ingredient could serve as the colloidal stabilizer. Examples of particulate inorganic materials are oxy compounds of at least one of calcium, magnesium, aluminum and silicon (or derivatives of such materials), such as silica, silicate, marble, clays and talc. Particulate inorganic materials can be natural or synthesized in reactors. The particulate inorganic material can be a mineral selected from, but not limited to, kaolin, bentonite, alumina, limestone, bauxite, gypsum, magnesium carbonate, calcium carbonate (ground or precipitated), perlite, dolomite, diatomite, huntite, magnesite, boehmita, sepiolite, paligorsquite, mica, vermiculite, illite, hydrotalcite, hectorite, halloysite and gibbsite. Other suitable clays (for example, aluminosilicates) include those that comprise the kaolinite, montmorillonite or illite mineral clay groups. Other specific examples are atapulgite, laponite and sepiolite.
    [0091] In one embodiment, the non-porous inorganic particulate materials are distributed within the polymeric particles with the cyclopropene complex to serve as a barrier for optional diffusion. The diffusion barrier is prepared by suspending such materials with the cyclopropene complex in the non-aqueous curable liquid mixture that is used to prepare the polymer particles of thermoplastic or thermosetting resin that serve as the dispersed phase b). Suitable particulate diffusion barrier materials include carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, mica and clays. It is possible that the same particulate inorganic material may be used for this Petition 870180014706, of 02/23/2018, p. 38/52
    35/39 bilize the emulsion and act as a barrier to diffusion.
    [0092] In one aspect of the invention, the particulate inorganic material is kaolin clay. Kaolin clay is also called china clay or water kaolin, and contains predominantly the mineral kaolinite (Al 2 Si 2 O 5 (OH) 4 ), a hydro aluminum silicate (or aluminosilicate).
    [0093] In one aspect of the invention, the particulate inorganic material may have the surface modified. Having the surface modified means that the surface of the inorganic particle has been modified to have reactive groups. The surface of the particles can be modified using a wide variety of chemicals, with the general structure X --- Y --- Z, where X is a chemical fraction with high affinity for the surface of the particles; Z is a chemical (reactive) fraction with a desired functionality; and Y is a chemical fraction that joins X to Z.
    X can be, for example, an alkoxy silane group such as triethoxysilane or trimethoxysilane or trichlorosilane, which is particularly useful when the particles have silanol (SiOH) groups on their surface. X can also be, for example, an acidic group (such as an acrylic or carboxylic acid group) which is particularly useful when the particles have basic groups on their surface. X can also be, for example, a basic group (such as an amine group), an epoxy group or an unsaturated group (such as an acrylic or vinyl group).
    Y can be any chemical group that joins X to Z, for example, a polyamide, a polyisocyanate, a polyester or an alkylene chain; more appropriately it is an alkylene chain; and even more appropriately it is a C 2-6 alkylene chain, such as ethylene or propylene.
    [0094] The reactive Z groups can be selected from any
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    36/39 groups, and can be different from Y, which can be used to react with a crosslinker.
    [0095] The type and amount of colloidal solid are selected in order to provide acceptable physical stability of the composition during curing. This can be quickly determined by a person skilled in the art by routinely evaluating a variety of compositions containing different amounts of this component. For example, the ability of colloidal solids to stabilize the composition can be verified by preparing a test sample with the colloidal solid and it can be confirmed that the emulsion of curable droplets is stable and does not exhibit any coalescence. Coalescence is apparent by the formation of large droplets visible to the naked eye, and finally by the formation of a layer of liquid monomers within the formulation. The physical stability of the composition during curing is acceptable if there is no evidence of significant coalescence and solid polymeric particles are present in the form of a fine dispersion.
    [0096] For example, in one embodiment, colloidal solids are used in an amount of 1 to 80%, particularly 4 to 50% by weight of the dispersed phase. Mixtures of colloidal solids can be used.
    [0097] The following examples further illustrate some aspects of the invention, but are not intended to limit its scope. Where not specified otherwise in this specification and in the claims, percentages are by weight.
    Examples 1 to 5
    Preparation of formulation [0098] The ingredients of the dispersed phase are pre-mixed with a shear mixer as described in table 1 below (HAIP is a complex of α-cyclodextrin and 1-MCP in the form of a
    Petition 870180014706, of 02/23/2018, p. 40/52
    37/39 powder. HAIP contains approximately 4.5% by weight of 1-MCP. (AgroFresh, Inc., Pa)), epoxy resin 635 Thin Epoxy Resin and epoxy hardener 556 Epoxy Hardener (2: 1) (Reichhold, Inc., NC). The continuous phase is pre-mixed according to table 1 with a low shear mixer. The pre-mixed dispersed phase is added to the pre-mixed continuous phase, and then mixed with a high shear mixer for 5 to 10 minutes. To accelerate the epoxy curing reaction, the mixed formulation was treated with a high temperature (70 ° C) for 3 hours. The components of control example 3 below were simply homogenized in a high shear mixer.
    MCP release rate [0099] The formulation was diluted in water (25 ppm MCP in water) with appropriate emulsifiers (Kinetic, Toximul TA-6, Stepfac 8180 and Toximul 8320, etc.) in a sealed bottle and then agitated. The release of MCP was monitored by gas chromatography analysis of the concentration of MCP in the free space of the bottle.
    Epinastia test [00100] The formulation was diluted in water (20 ppm MCP in water) with appropriate emulsifiers (Kinetic, Toximul TA-6, Stepfac 8180 and Toximul 8320, etc.) followed by spraying on tomato plants. Etefon was applied 1 hour after treatment with 1-MCP. The angle between the 3rd petiole and the plant stem was measured before applying 1-MCP and again 24 hours after treatment. The final data are expressed as the average variation of the angle between the 3rd petiole and the stem.
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    38/39
    Table 1:
    Example 1 Example 2 Example 3 Phasescattered HAIP 5%Epoxy 635 13.4%Hardener 556 6.6% HAIP 10%Epoxy 635 10%Hardener 5565% HAIP 5% Continuous phase Aerosil R972 5%IsoparV 70% Aerosil R972 5%IsoparV 69%AL-22 1% AL-22 0.5%IsoparV 94.5% Average diameter ofparticles (pm) 85 55 10 MCP concentrationin free spaceIn 1 hourIn 2 hoursIn 4 hours 108 ppm201 ppm380 ppm 450 ppm850 ppm1400 ppm 12,000 ppm14,000 ppm14,000 ppm Epinastia testAngle variation ofleaf Not tested 11th 22 °
    Table 2 Examples 4 and 5
    Example 4 Example 5 Phasescattered HAIP 5%Phenol resinformaldehyde 20%Phenol sulfonic acid1% HAIP 5%Ester resinvinyl 20% Continuous phase Aerosil R972 5%IsoparV 69% Aerosil R972 5%IsoparV 70% MCP concentrationin free spaceIn 1 hourIn 2 hours 1350 ppm1470 ppm 452 ppm616 ppm
    [00101] Examples 1, 2, 4 and 5 illustrate that the compositions of
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    39/39 the present invention results in less degradation and loss of 1-MCP from the molecular complex and provides improved resistance to stress responses induced by ethylene compared to the control of example 3.
    Example 6
    Preparation of formulation [00102] Pre-mix the dispersed phase with a high shear mixer. Pre-mix the continuous phase with a low shear mixer. Add the pre-mixed dispersed phase to the continuous phase, and then mix with a high shear mixer for 5 to 10 minutes. To accelerate the epoxy curing reaction, the mixed formulation was treated with a high temperature (70 ° C) for 3 hours.
    B. Release rate [00103] The formulation was diluted in water with an appropriate surfactant and then kept in an orbital shaker. The samples were collected at appropriate time intervals. The release rate was monitored by chromatography analysis.
    6 Phase HAIP 10% scattered BPA epoxy resin (bisphenol-A diglycidyl ether) 10%Poly (oxypropylene) diamine 5% Continuous phase Aerosil R972 5%IsoparV 70%
    [00104] Although only a few exemplary embodiments of that invention have been described in detail above, those skilled in the art will quickly find that many modifications are possible in the exemplary embodiments without departing materially from the new teachings and advantages of that invention. Thus, it is intended that all such modifications are included within the scope of that invention as defined in the following claims.
    Petition 870180014706, of 02/23/2018, p. 43/52
    1/4
    权利要求:
    Claims (20)
    [1]
    1. Liquid, non-aqueous concentrated dispersion composition, characterized by the fact that it comprises:
    (a) a liquid continuous phase, non-aqueous and substantially immiscible in water, that is, which forms two phases when mixed with water in a concentration of less than 10% by weight, the liquid continuous phase selected from vegetable oils, silicone oils, methylated vegetable oils, refined paraffin hydrocarbons, mineral oils and mixtures thereof, comprising 5% by weight of Aerosil R972, 69-70% by weight of IsoparV, and 1% of AL-22;
    (b) a dispersed solid phase, comprising polymeric particles prepared from a polymerizable or curable thermoplastic or thermoset resin, and comprising 5% by weight of HAIP, 20% by weight of phenolformaldehyde resin, 1% by weight of acid phenol-sulfonic, and 20% by weight of vinyl ester resin, the outer surfaces of the particles comprising a solid colloidal material selected from carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers , silica and clays, and the particles have at least one complex of 1-methylcyclopropene and a molecular encapsulating agent distributed in them.
    [2]
    2. Composition according to claim 1, characterized by the fact that the solid colloidal material is present to stabilize the polymeric particles in an emulsion state during the process used to prepare the dispersed phase.
    [3]
    Composition according to claim 1, characterized in that the complex of an alkylcyclopropene and a molecular encapsulating agent is a complex of α-cyclodextrin and 1methylcyclopropene.
    Petition 870180015177, of 02/26/2018, p. 5/12
    2/4
    [4]
    4. Composition according to claim 1, characterized by the fact that the dispersed phase comprises at least one mobile non-cross-linkable chemical, which is selected from the group consisting of: an α-olefin and an N-vinylpyrrolidone, copolymers of alkylated vinylpyrrolidone or α-olefin and ethylene glycol copolymers, so that the extraction of that chemical from the dispersed phase makes it porous to allow the cyclopropene to diffuse at a controlled rate.
    [5]
    5. Composition according to claim 1, characterized by the fact that the continuous phase (a) further comprises at least one agrochemically active ingredient.
    [6]
    6. Composition, according to claim 1, characterized by the fact that (a) also comprises one or more surfactants or dispersants.
    [7]
    7. Composition, according to claim 1, characterized by the fact that (b) also comprises a particulate inorganic material distributed within the polymeric particles.
    [8]
    8. Composition, according to claim 1, characterized by the fact that (b) comprises a polymeric matrix of cured epoxy resin prepared from the curing of an epoxy resin selected from di- and polyiepoxyl monomers, prepolymers or mixtures of these with a hardener selected from primary and secondary amines and their adducts, cyanamide, diciandiamide, polycarboxylic acids, polycarboxylic acid anhydrides, polyamines, polyaminoamides, polyamine ducts, polyols and mixtures thereof.
    [9]
    9. Composition, according to claim 4, characterized by the fact that the non-crosslinkable mobile chemical in the dispersed phase also functions as a surfactant or dispersant.
    [10]
    10. Method to regulate the growth of plants, characterPetition 870180015177, of 26/02/2018, p. 6/12
    3/4 terized by the fact that it is through the dilution of a concentrated composition, as defined in claim 1, with an aqueous liquid vehicle selected from water and liquid fertilizer, and application of the diluted composition in the plant species or location thereof.
    [11]
    11. Process for the preparation of a concentrated, non-aqueous liquid dispersion composition, as defined in claim 1, incorporating a cyclopropene complex, characterized by the fact that it comprises the steps of:
    (a) dissolving or suspending the cyclopropene complex in a non-aqueous liquid mixture comprising at least one curable thermoset resin, optionally at least one non-crosslinkable mobile chemical and, optionally, at least one non-porous particulate mineral;
    (b) emulsifying said solution or suspension in a water immiscible liquid containing a solid colloidal emulsion stabilizer; and (c) curing the mixture containing said at least one curable thermosetting resin to produce a dispersion of polymeric particles containing a cyclopropene complex in a water-immiscible liquid.
    [12]
    12. Process, according to claim 11, characterized by the fact that the thermoset resin is selected from epoxy, polyurea, polyurethane, aminoplastic resin, phenolic resin and polyester.
    [13]
    Process according to claim 11, characterized in that the cyclopropene complex is a complex of α-cyclodextrin and 1-methylcyclopropene.
    [14]
    14. Process according to claim 11, characterized by the fact that the mobile non-crosslinkable chemical is insoluble in water, soluble in water, a polymer, a copolymer, a surfactant, an acid or a base.
    Petition 870180015177, of 02/26/2018, p. 7/12
    4/4
    [15]
    15. Process according to claim 12, characterized by the fact that the thermoset resin is an epoxy resin.
    [16]
    16. Process according to claim 15, characterized in that the epoxy resin comprises a bisphenol A diglycidyl ether.
    [17]
    17. Process according to claim 15, characterized in that the curing of the epoxy resin is achieved using an amine hardener.
    [18]
    18. Process according to claim 17, characterized by the fact that curing is achieved using an amine hardener comprising a poly (oxypropylene) diamine.
    [19]
    19. Process according to claim 13, characterized by the fact that it is carried out in the presence of a colloidal solid selected from carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulphates, polymers, silica and clays .
    [20]
    20. Process according to claim 19, characterized by the fact that the colloidal solid is a hydrophobic pyrolyzed silica.
    Petition 870180015177, of 02/26/2018, p. 12/12
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    法律状态:
    2015-09-29| B15I| Others concerning applications: loss of priority|
    2015-11-24| B12F| Appeal: other appeals|
    2017-11-28| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2017-11-28| B15K| Others concerning applications: alteration of classification|Ipc: A01N 27/00 (1980.01), A01N 25/02 (1980.01), A01N 2 |
    2018-03-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-05-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US35225210P| true| 2010-06-07|2010-06-07|
    US61/352,252|2010-06-07|
    PCT/US2011/039461|WO2011156388A1|2010-06-07|2011-06-07|Cyclopropene compositions|
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