TW201534217A - Methods and compositions of granule formulations - Google Patents

Abstract

This invention is related to granule formulations of a molecular complex comprising a volatile compound, where no adjuvant/binder is required in such granule formulations. In addition, it is surprising that use of molecular sieve destabilizes the granule formulations provided herein, thus no molecular sieve is required. Provided are methods for preparing granule formulations of a molecular complex comprising a volatile compound, and compositions comprising such granule formulations. In addition, methods of treating plant or plant parts using compositions disclosed herein are also provided.

Description

Method and composition of particle formulation Field of invention

The present invention relates to methods and compositions for particle formulations.

Background of the invention

Sometimes, it is necessary to use a cyclopropene compound to enhance the growth of crop plants. The method disclosed in U.S. Patent Application No. 2007/0165166 relates to contacting a crop plant with a composition containing a cyclopropene compound. In the example of U.S. Patent Application No. 2007/0165166, the contact is effected by spraying a liquid composition on the plant. Liquid compositions containing cyclopropene compounds have some disadvantages in use. Special equipment, such as spraying equipment, is required when using liquid compositions, and sometimes it is not possible to obtain them. At the same time, the liquid composition is typically stored in a closed tank or other closed container. If the liquid composition contains a volatile cyclopropene compound, it may accumulate a high concentration of volatile organic compounds in the upper void of the closed vessel, which may cause a hazard.

The application of gaseous compositions on crop plants in farmland also has disadvantages. When applied in open field, the gaseous composition will diffuse into the atmosphere, with little or no effect on the rice plant.

Rice is the seed of the monocotyledon of Oryza . The term "rice" as used in this application refers to the harvested rice seed or to a rice plant on which the seed has been grown or will be grown. The two main rice species currently cultivated are cultivated rice ( Oryza sativa L.) and West African cultivated rice ( Oryza glaberrima Steud). Rice is an important crop. There is a need to provide a process that uses cyclopropene compounds to enhance the growth of rice and/or other plants while avoiding one or more of the above disadvantages.

Summary of invention

The present invention is directed to a particulate formulation of a molecular complex comprising a volatile compound, wherein the particulate formulation does not require an adjuvant/adhesive. Moreover, the use of molecular sieves unexpectedly renders the particle formulation provided by the present application unstable, thus eliminating the need for molecular sieves. A method is provided for preparing a particulate formulation comprising a molecular compound comprising a volatile compound: and providing a composition comprising the particulate formulation. In addition, methods of treating plants or plant parts using the compositions disclosed herein are also provided.

In one aspect, a particle formulation is provided comprising (a) a molecular complex consisting of a volatile compound and a molecular encapsulating agent; and (b) a carrier component, the carrier component The moisture content is between 5% and 35%.

In one embodiment, the moisture content is between 7% and 15%, or between 8% and 12%. In another embodiment, the moisture content is at least 10%. In another embodiment, the moisture content is about 10%.

In another embodiment, the carrier component comprises clay. In another In an embodiment, the carrier component comprises bentonite, limestone, or a combination thereof. In another embodiment, the carrier component comprises a sodium bentonite clay. In another embodiment, the particulate formulation does not comprise a binder component.

In another embodiment, the chemical stability of the molecular complex is improved compared to a control formulation without a carrier component; and the carrier component has a moisture content of between 5% and 35%. between. In another embodiment, the chemical stability of the molecular complex is increased by at least two fold. In another embodiment, the chemical stability of the molecular complex is increased by two to five times. In another embodiment, the molecular complex is improved in chemical stability at room temperature, at 54 ° C, or both.

In another embodiment, the volatile compound comprises a cyclopropene compound having the formula: Wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or naphthyl group; wherein the substituents are independently halogen, alkoxy Or a substituted or unsubstituted phenoxy group. In one embodiment, R is a C _1-8 alkyl group. In another embodiment, R is methyl.

In another embodiment, the volatile compound comprises a cyclopropene compound having the formula: Wherein R ¹ is a substituted or unsubstituted C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkenyl group, a C ₁ -C ₄ alkynyl group, a C ₁ -C ₄ cycloalkyl group, a cycloalkylalkyl group And phenyl or naphthyl; and R ² , R ³ and R ⁴ are hydrogen. In another embodiment, the cyclopropene compound comprises 1-methylcyclopropene (1-MCP).

In another embodiment, the particulate formulation comprises between 1-5% and 10%, between 0.3% and 3% or between 0.5% and 1.5%. In another embodiment, the molecular encapsulating agent is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof. In another embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin.

In another aspect, a method is provided for stabilizing a molecular complex consisting of a volatile compound and a molecular encapsulating agent; the method comprising preparing a particulate formulation using a carrier component, the carrier component The moisture content is between 5% and 35%.

In one embodiment, the moisture content is between 7% and 15%, or between 8% and 12%. In another embodiment, the moisture content is at least 10%. In another embodiment, the moisture content is about 10%.

In another embodiment, the carrier component comprises clay. In another embodiment, the carrier component comprises bentonite, limestone, or a combination thereof. In another embodiment, the carrier component comprises a sodium bentonite clay. In another embodiment, the particulate formulation does not comprise a binder component.

In another embodiment, the chemical stability of the molecular complex is improved compared to a control formulation without a carrier component; and the carrier component has a moisture content of between 5% and 35%. between. In another embodiment, the chemical stability of the molecular complex is increased by at least two fold. In another reality In the examples, the chemical stability of the molecular complex is increased by two to five times. In another embodiment, the molecular complex is improved in chemical stability at room temperature, at 54 ° C, or both.

In another embodiment, the volatile compound comprises a cyclopropene compound having the formula: Wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or naphthyl group; wherein the substituents are independently halogen, alkoxy Or a substituted or unsubstituted phenoxy group. In one embodiment, R is a C _1-8 alkyl group. In another embodiment, R is methyl.

In another embodiment, the volatile compound comprises a cyclopropene compound having the formula: Wherein R ¹ is a substituted or unsubstituted C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkenyl group, a C ₁ -C ₄ alkynyl group, a C ₁ -C ₄ cycloalkyl group, a cycloalkylalkyl group And phenyl or naphthyl; and R ² , R ³ and R ⁴ are hydrogen. In another embodiment, the cyclopropene compound comprises 1-methylcyclopropene (1-MCP).

In another embodiment, the particulate formulation comprises between 1-5% and 10%, between 0.3% and 3% or between 0.5% and 1.5%. In another embodiment, the molecular encapsulating agent is selected from the group consisting of alpha-rings A group consisting of dextrin, β-cyclodextrin, γ-cyclodextrin, or a combination thereof. In another embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin.

In another aspect, a method for preparing a particle formulation as described herein is provided. The method comprises using a milling process and a carrier component having a moisture content of between 5% and 35%.

In one embodiment, the roller compaction method does not use a binder. In another embodiment, the milling process does not use molecular sieves.

In another aspect, a method of increasing crop yield and/or protection crops is provided, comprising applying a particle formulation provided by the present application to a field planted with the crop, wherein the crop plant line is in a reproductive or maturity phase.

In one embodiment, the crop is selected from the group consisting of rice, corn, wheat, soybean, canola, and cotton. In another embodiment, the particulate formulation comprises 1-methylcyclopropene (1-MCP). In another embodiment, the application rate of 1-MCP is between 10 grams of active ingredient per hectare and 100 grams of active ingredient per hectare, between 20 grams of active ingredient per hectare and 70 grams of active ingredient per hectare. Or between 40 grams of active ingredient per hectare to 60 grams of active ingredient per hectare. In another embodiment, the application rate of 1-MCP is about 50 grams of active ingredient per hectare.

Figure 1 shows a representative milling process for use in the granular formulation described in this application.

Figure 2 shows representative results (curve average) of the effect of moisture on degradation at 54 °C.

Figure 3 shows representative results (curve average) of the effect of the binder on degradation.

Figure 4 shows a representative release rate of 1-MCP of a formulation containing bentonite. Samples L, M and N contained 0.1% 1-MCP, while samples O and P contained 0.5% 1-MCP.

Figure 5 shows a representative correlation between the dissolution rate of particles immersed in water and the percentage of 1-MCP.

Figure 6 shows representative data from the upper void of 0.5% 1-MCP in sodium bentonite particles.

Detailed description of the invention

The present invention is based on the fact that the particle formulation of the molecular complex comprising a volatile compound does not require the unexpected result of an adjuvant/adhesive. Furthermore, it has been unexpectedly discovered that the use of molecular sieves renders the particle formulation provided by this application unstable and therefore does not require molecular sieves. A method of preparing a particulate formulation comprising a molecular compound comprising a volatile compound; and providing a composition comprising the formulation of the particle. Methods of treating plants or plant parts using the compositions disclosed herein are also provided.

Solid particles are characterized by their particle size. If the particles are not spherical, the diameter of the sphere having the same volume as the particle is the particle diameter.

It is sometimes desirable to formulate the product in a dry state to avoid the use of water. Pressing (or granulation) is a process that expands the size of the powder material into a sheet with or without the use of a binder. Ensure the adhesion of the material by the mechanical pressure exerted on the product by the pressing equipment Hehe. The sheet is then crushed and sieved to produce a product in the form of particles of the desired size.

The compression/granulation process is an alternative to wet agglomeration, which is a wider variety of materials that can be agglomerated than other processes and provides a specified range of product constant sizes. The capacity of the pressing/granulation unit is generally from 50 kg/hr to 100 t/hr.

Rolling is a dry granulation process in which many factors need to be considered, controlled and optimized; for example, choice of carrier and binder, roll pressure, roll speed and feed rate of the starting material. These factors determine the nature of the product (such as the formation of a ribbon) and the nature of the final particles. Important product qualities such as density of the ribbon, flowability, compressibility of the particles, and strength of the finished article are highly dependent on the above parameters.

Controlling these factors is critical to achieving the desired quality of the product. A thorough understanding of the chemical and physical properties of the starting materials as well as the process parameters is also essential. A wealth of literature on suppression methods can be found. However, most agrochemical applications are limited to the formulation of fertilizers.

In the present application, including the specification and the scope of the patent application, the following terms used have the definitions shown below unless otherwise indicated. It must be noted that the singular forms "a", "the", and "the" The definition of standard chemical terms can be found in the reference book, including "Advanced Organic Chemistry", fourth edition, published by Carey and Sundberg, published by Plenum Press, New York, USA. (2000) and B (2001).

The term "group" as used in this application refers to a particular fragment or functional group of a molecule. A chemical group is usually a chemical entity that is recognized to be embedded or attached to a molecule.

The term "alkyl" as used in this application, refers to an unsubstituted or substituted hydrocarbon group, and may include straight chain, branched, cyclic, saturated, and/or unsaturated forms. Although the alkyl group may be an "unsaturated alkyl" group, it is meant to contain at least one alkene or alkyne group; the alkyl group is typically a "saturated alkyl group" which means that it does not contain any A olefin or alkyne group. Likewise, although the alkyl group can be cyclic, the alkyl group is typically a non-cyclic group. Thus, in some embodiments, "alkyl" refers to a selectively substituted straight or alternatively substituted branched saturated hydrocarbon monoradical; in some embodiments, it has from about 1 to about 30 carbon atoms; in some embodiments, from about 1 to about 15 carbon atoms; and in other embodiments, from about 1 to about 6 carbon atoms. Examples of saturated alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl- 1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3- Methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2, 2-Dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, butyl, isobutyl, sec-butyl, tert-butyl, N-pentyl, isopentyl, neopentyl and n-hexyl, and long-chain alkyl such as heptyl and octyl. Although this definition also encompasses "alkyl" values that do not specify a range of values, it should be noted that whenever a range of values appears in the present application, such as "1 to 6", it is intended to mean each integer in the range indicated; "1 to 6 carbon atoms" or "C _1-6 " or "C ₁ -C ₆ " means that the alkyl group may be 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 It consists of one carbon atom and/or six carbon atoms.

The term "substituted alkyl" as used in this application, refers to an alkyl group, as defined in the present application, wherein one or more (up to about 5 and preferably up to about 3) hydrogen atoms are Substituent substitution, the substituents are independently selected from the group of substituents as defined in the present application.

The terms "substituent" and "substituted" as used in this application, refer to a group that can be used to substitute another group on one molecule. Such groups are known in the art Chemistry Department of skill, and can include, but are not limited to the following independently selected groups, or designated subset of one or more of: _{halo, -CN, -OH, -NO 2,} -N 3 , =O, =S, =NH, -SO ₂ , -NH ₂ , -COOH, -S(O ₂ ), nitroalkyl, amine groups, and including monosubstituted and disubstituted amine groups, cyanato Base, isocyanato group, thiocyanyl group, isocyanato group, sulfhydryl group, O-amine methyl sulfhydryl group, n-aminomethyl hydrazino group, amine thiomethenyl group, urea group, isourea group, thiourea group, different Thiourea, fluorenyl, sulfonyl, sulfinyl, sulfo, sulfonylamino, phosphonium, phospholipid, phosphonium, dialkylamine, diarylamine, diaryl Alkylamino group; and a protected compound thereof. Protecting groups which form a protected compound consisting of the above substituents are known to those skilled in the art and can be found in references such as John Wiley & Sons, Inc., New York, NY, USA (1999) And the third edition of "Protective Groups In Organic Synthesis" by Greene and Wuts and published by Thieme Verlag, New York, NY (1994) And "Protective Groups" by Kocienski, et al., the entire contents of which are incorporated herein by reference.

The term "alkoxy" as used in this application refers to -O-alkyl, wherein alkyl is as defined in the present application. In one embodiment, the alkoxy group includes, for example, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy, hypo-butoxy, n-pentyloxy , n-hexyloxy, 1,2-dimethylbutoxy and the like. The alkoxy group can be unsubstituted or substituted.

The terms "ring" and "member ring" as used in this application refer to any cyclic structure including alicyclic, heterocyclic, aryl, heteroaromatic, and the like as described in this application. Ring fused or non-fused ring system. The term "member" is used to indicate the number of skeletal atoms that make up the ring. Thus, for example, pyridine, piperazine and pyrimidine are six-membered rings, while pyrrole, tetrahydrofuran and thiophene are five-membered rings.

The term "aromatic" as used in this application refers to a cyclic or polycyclic group having a conjugated unsaturated (4n+2) π electronic system (where n is a positive integer), sometimes It is called a non-localized π electronic system.

The term "aryl" as used in this application refers to a selectively substituted aromatic cyclic hydrocarbon monoradical having from 6 to about 20 ring atoms, preferably from 6 to about 10 carbons. Atoms, and include fused (or condensed) and non-fused aromatic rings. The fused aromatic cyclic radical contains 2 to 4 fused rings in which the attached ring is an aromatic ring, and the other individual rings in the fused ring may be a cycloalkyl group, a cycloalkenyl group, or a ring. Alkynyl, heterocycloalkyl, Heterocyclenyl, heterocycloalkynyl, aryl, heteroaromatic or any combination thereof. Non-limiting examples of monocyclic aryl groups include phenyl; a fused ring aryl group including a naphthyl group, an anthracenyl group, an anthracenyl group; and a non-fused diaryl group including a biphenyl group.

The term "substituted aryl" as used in this application refers to an aryl group as defined in the present application wherein one or more (up to about 5 and preferably up to about 3) hydrogen atoms are Substituted by a substituent which is independently selected from the group as defined in the present application (unless otherwise limited in the definition of aryl substituent).

The term "heteroaryl" as used in this application, refers to a selectively substituted aromatic cyclic mono radical having from about 5 to about 20 backbone ring atoms, preferably from 5 to about 10 ring atoms, and including fused (or condensed) and non-fused aromatic rings, and having one or more (1 to 10 and preferably about 1 to about 4) ring atoms, the ring atom system An atom other than carbon (ie, a hetero atom) such as oxygen, nitrogen, sulfur, selenium, phosphorus, or a combination thereof. The term heteroaryl includes both selectively substituted fused and non-fused heteroaryl radicals having at least one heteroatom. The fused heteroaryl radical may contain from 2 to 4 fused rings wherein the attached ring is a heteroaromatic ring and the other individual rings in the fused ring system may be alicyclic, heterocyclic, aromatic A base, a heteroaryl group or any combination thereof. The term heteroaryl also includes fused and non-fused heteroaryl groups having from 5 to about 12 backbone ring atoms, as well as those having from 5 to about 10 backbone ring atoms. Examples of heteroaryl groups include, but are not limited to, acridinyl, benzo[1,3]dioxime, benzimidazolyl, benzoxazolyl, benziso Azolyl, benzoxazolyl, benzofuranyl, benzofurazyl, benzopipetanyl, benzothiadiazolyl, benzothiazolyl, benzo[b]thienyl, benzophenylthio Benzothiopyranyl, benzotriazolyl, benzo Azyl, carbazolyl, porphyrin, Alkenyl, Orolinyl, furanyl, furfuryl, furopyridinyl, furyl, imidazolyl, oxazolyl, fluorenyl, decyl, fluorene Base, isobenzofuranyl, isodecyl, iso Azyl, isoquinolyl, isothiazolyl, naphthyl, Pyridyl, Diazolyl, Azolyl, brown Thiophene Base Base Thio group, thiol group, phenanthryl group, phenanthroline group, hydrazine Base, acridinyl, fluorenyl, puteridinyl, pyridyl Base, pyrazolyl, pyridyl, pyridinyl, anthracene Base Pyrimidinyl, pyrimidyl, pyrrolyl, quinazolinyl, quinolinyl, quin Lolinyl, tetrazolyl, thiadiazolyl, thiazolyl, thienyl, tri And (1,2,3,)-triazolyl and (1,2,4)-triazolyl, etc., and, as appropriate, oxides thereof, such as pyridyl-N-oxide.

The term "substituted heteroaryl" as used in this application, refers to a heteroaryl group as defined in the present application, wherein one or more (up to about 5 and preferably up to about 3) hydrogen atoms. Substituted by a substituent selected independently from the group as defined in the present application.

The term "debonding group" as used in the present application refers to a group having the meanings conventionally given in synthetic organic chemistry, that is, one atom or one group may be substituted under the substitution reaction conditions. Examples of leaving groups include, but are not limited to, halogen; alkanesulfonyloxy or arylenesulfonyloxy, such as methanesulfonyloxy, ethanesulfonyloxy, methylthio, benzenesulfonyloxy, toluenesulfonate Oxyl and thienyloxy; dihalophosphonium oxy; optionally substituted benzyloxy, isopropoxy, decyloxy and the like. In some embodiments, the leaving groups may be HC (O) -COOH, or RC (O) -COOH, wherein R is a C ₁ -C ₆ alkyl or substituted C ₁ -C ₆ alkyl.

The compounds of the invention as described in the present application can be synthesized using standard synthetic techniques known to those skilled in the art, or using techniques known in the art in combination with the methods described herein. Available from commercial sources such as Aldrich Chemical Company (Milwaukee, Wisconsin, USA), Sigma Chemical Company (St. Louis, Missouri, USA) for synthesis as in this application The starting material of the compound of the invention or the self-synthesis starting material. The compounds described in this application and other related compounds having different substituents can be synthesized using techniques and materials known to those skilled in the art, such as John Wiley & Sons, for example, New York, NY, USA. The company published (1992) and the fourth edition of "Advanced Organic Chemistry" by March; published by Carey and Sundberg, published by Plenum Press, New York, USA Advanced Organic Chemistry, Fourth Edition, Volume A (2000) and B (2001); and published by John Wiley & Sons, New York, NY (1999) The third edition of the "Protective Groups In Organic Synthesis" by Greene and Wuts, the entire contents of which are incorporated herein by reference. The general methods for preparing the compounds disclosed in this application can be derived from known reactions in the art, and as known to those skilled in the art, such reactions can be modified by the use of suitable reagents and conditions. To introduce the application provided in this application Various groups as seen in the chemical formula. For example, the compounds described in this application can be modified with various electrophiles or nucleophiles to form new functional groups or substituents.

The practice of the invention involves the use of one or more cyclopropene compounds. The cyclopropene compound as used in the present application is any compound of the following formula: Wherein each of R ¹ , R ² , R ³ and R ⁴ is independently selected from the group consisting of hydrogen and a chemical group having the formula: -(L) _n -Z wherein n is from 0 to 12 An integer. Each L is a divalent radical. Suitable L groups include, for example, those containing one or more atoms selected from the group consisting of hydrogen, boron, carbon, nitrogen, oxygen, phosphorus, sulfur, ruthenium or mixtures thereof. The atoms in the L group may be bonded to each other by a single bond, a double bond, a triple bond, or a mixture thereof. Each L group may be linear, branched, cyclic, or a combination thereof. In any of the R groups (i.e., any of R ¹ , R ² , R ³ and R ⁴ ), the total number of hetero atoms (i.e., atoms other than hydrogen and carbon) is from 0 to 6. Further, the total number of non-hydrogen atoms in any of the R groups is 50 or less. Each of Z is a monovalent radical. Each Z series is independently selected from the group consisting of hydrogen, halo, cyano, nitro, nitroso, azide, chlorate, bromate, iodate, isocyanato, isocyano, isocyanide A group consisting of a thio group, a pentafluorothio group, and a chemical group G, wherein G is a ring system of 3 to 14 members.

The R ¹ , R ² , R ³ and R ⁴ groups are independently selected from suitable groups. Among such groups, a group suitable as one or more of R ¹ , R ² , R ³ and R ⁴ is, for example, an aliphatic group, an aliphatic oxy group, an alkylphosphonium oxy group, a cycloaliphatic group. Alkyl, cycloalkylsulfonyl, cycloalkylamino, heterocyclyl, aryl, heteroaryl, halogen, fluorenyl, other groups, and mixtures and combinations thereof. Groups suitable as one or more of R ¹ , R ² , R ³ and R ⁴ may be substituted or unsubstituted.

Suitable R ¹ , R ² , R ³ and R ⁴ groups include, for example, aliphatic groups. Some suitable aliphatic groups include, for example, alkyl, alkenyl and alkynyl groups. Suitable aliphatic groups can be straight chain, branched, cyclic, or a combination thereof. Additionally, suitable aliphatic groups can be substituted or unsubstituted.

As in the present application, if one or more hydrogen atoms of a chemical group in question are substituted by a substituent, the chemical group is referred to as "substituted".

Suitable R ¹ , R ² , R ³ and R ⁴ groups, for example, also include substituted and unsubstituted heterocyclic groups which are bonded to the cyclopropene compound via an intermediate oxy, amine, carbonyl or sulfo group. Illustrative; examples of such R ¹ , R ² , R ³ and R ⁴ groups are heterocyclic oxy, heterocyclic carbonyl, diheterocyclic amino and diheterocyclic sulfo.

Suitable R ¹ , R ² , R ³ and R ⁴ groups, for example, also include substituted and unsubstituted heterocyclic groups which are via an intermediate oxy, amine, carbonyl, sulfo, thioalkyl or An aminosulfonyl group bonded to a cyclopropene compound; examples of such R ¹ , R ² , R ³ and R ⁴ groups are a diheteroarylamino group, a heteroarylsulfanyl group and a diheteroarylaminosulfonyl group. .

Suitable R ¹ , R ² , R ³ and R ⁴ groups also include, for example, hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, nitroso, azide, chlorate, Bromo acid group, iodate group, isocyanato group, isocyano group, isocyanothio group, pentafluorothio group; ethoxycarbonyl group, ethoxycarbonyl group, cyanooxy group, nitric acid group, nitrite group, perchloric acid , alkadienyl, butyl fluorenyl, diethylphosphonium oxy, dimethylphenyl fluorenyl, isoquinolyl, fluorenyl, naphthyl, phenoxy, phenyl, piperidinyl, pyridyl , quinolyl, triethylsulfonyl, trimethylsulfonyl; and substituted analogs thereof.

The chemical group G as used in this application is a ring system of 3 to 14 members. Suitable ring systems for the chemical group G may be substituted or unsubstituted; they may be aromatic (for example including phenyl and naphthyl) or aliphatic (including unsaturated aliphatic, partially saturated aliphatic or saturated fat) Family); and the like may be carbocyclic or heterocyclic. Some suitable heteroatoms among the heterocyclic G groups include, for example, nitrogen, sulfur, oxygen, and combinations thereof. A ring system suitable as the chemical group G may be a monocyclic, bicyclic, tricyclic, polycyclic, spiro or fused ring; in a ring system of a bicyclic, tricyclic or fused ring of a suitable chemical group G, a single chemical group G Each of the rings may be of the same type or of two or more types (for example, an aromatic ring may be fused to an aliphatic ring).

In one embodiment, one or more of R ¹ , R ² , R ³ and R ⁴ are hydrogen or (C ₁ -C ₁₀ )alkyl. In another embodiment, each of R ¹ , R ² , R ³ and R ⁴ is hydrogen or (C ₁ -C ₈ )alkyl. In another embodiment, each of R ¹ , R ² , R ³ and R ⁴ is hydrogen or (C ₁ -C ₄ )alkyl. In another embodiment, each of R ¹ , R ² , R ³ and R ⁴ is hydrogen or methyl. In another embodiment, R ¹ is (C ₁ -C ₄ )alkyl, and each of R ² , R ³ and R ⁴ is hydrogen. In another embodiment, R ¹ is methyl, and each of R ² , R ³ and R ⁴ is hydrogen, and the cyclopropene compound is referred to herein as 1-methylcyclopropene or "1- MCP".

In another embodiment, the cyclopropene compound has the following chemical formula: Wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or naphthyl group; wherein the substituents are independently halogen, alkoxy Or a substituted or unsubstituted phenoxy group. In one embodiment, R is a C _1-8 alkyl group. In another embodiment, R is methyl.

In another embodiment, the cyclopropene compound has the following chemical formula: Wherein R ¹ is a substituted or unsubstituted C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkenyl group, a C ₁ -C ₄ alkynyl group, a C ₁ -C ₄ cycloalkyl group, a cycloalkylalkyl group And phenyl or naphthyl; and R ² , R ³ and R ⁴ are hydrogen. In another embodiment, the cyclopropene comprises 1-methylcyclopropene (1-MCP).

The boiling point of the cyclopropene compound used in the examples at 1 atm is preferably 50 ° C or lower, more preferably 25 ° C or lower, still more preferably 15 ° C or lower. Further, the cyclopropene compound used in the examples preferably has a boiling point of -100 ° C or higher, more preferably -50 ° C or higher, more preferably -25 ° C or higher, at a boiling point of 1 atm. Good is above 0 °C.

The compositions of the present invention comprise at least one molecular encapsulating agent which encapsulates one or more cyclopropene compounds or encapsulates a portion of one or more cyclopropene compounds. A molecular complex comprising a cyclopropene compound molecule or a portion of a cyclopropene compound molecule encapsulated in one molecule of a molecular encapsulating agent is referred to herein as a "cyclopropene compound complex".

In a preferred embodiment, at least one cyclopropene compound complex present is an inclusive complex. In the intrinsic composite, the molecular encapsulating agent forms a cavity, and a portion of the cyclopropene compound or cyclopropene compound is located within the cavity.

In the inclusion complexes, the interior of the cavity of the molecular encapsulating agent is preferably substantially non-polar or hydrophobic or both, and the cyclopropene compound (or the portion of the cyclopropene compound located in the cavity) ) is also substantially non-polar or hydrophobic or both. It is contemplated that in the non-polar cyclopropene compound complex, van der Waals or hydrophobic interactions or both may cause the cyclopropene compound molecules or portions thereof to be long before the invention is not limited by any particular theory or mechanism. The time stays in the cavity of the molecular encapsulant.

The amount of molecular encapsulating agent is generally recited by the ratio of the molar number of the molecular encapsulating agent to the molar number of the cyclopropene compound. In a preferred embodiment, the ratio of the number of moles of the molecular encapsulating agent to the number of moles of the cyclopropene compound is 0.1 or more, more preferably 0.2 or more, still more preferably 0.5 or more, still more preferably 0.9 or more. Further, in a preferred embodiment, the ratio of the molar number of the molecular encapsulating agent to the molar number of the cyclopropene compound is 10 or less, more preferably It is 5 or less, more preferably 2 or less, still more preferably 1.5 or less.

Suitable molecular encapsulating agents include, for example, organic and inorganic molecular encapsulating agents. Preferred are organic molecular encapsulating agents, including, for example, substituted cyclodextrins, unsubstituted cyclodextrins, and crown ethers. Suitable inorganic molecular encapsulating agents include, for example, zeolites. Mixtures of suitable molecular encapsulating agents are also suitable. In a preferred embodiment, the encapsulating agent is alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin or a mixture thereof. A more preferred embodiment of the invention uses alpha-cyclodextrin.

The practice of the invention involves the use of a particulate composition. The particulate composition is a composition in the form of solid particles at 1 atm and at a temperature of 5 ° C to 40 ° C. The particle composition is a collection of solid particles, wherein more than 90% by weight of the aggregate is composed of particles having a particle diameter of 1 μm or more, and more than 90% of the aggregate weight thereof is composed of particles having a particle diameter of 5 cm or less. composition. More than 90% by weight of the aggregate is preferably composed of particles having a particle diameter of 10 μm or more. More than 90% by weight of the aggregate is also preferably composed of particles having a particle diameter of 1 cm or less.

In another aspect of the invention, there is provided a method of improving rice planting in a rice field, comprising adding a particulate composition to the water of the rice field, wherein the particle composition comprises encapsulation in a molecular encapsulating agent One or more cyclopropene compounds.

The particulate composition preferably contains 0.02% by weight or more of the cyclopropene compound based on the weight of the particulate composition. The content of the cyclopropene compound of the particulate composition is more preferably 0.05% by weight or more, still more preferably 0.09% by weight or more, based on the weight of the particulate composition. The particulate composition preferably contains less than 5% of the cyclopropene compound, based on the weight of the particulate composition. The content of the cyclopropene compound of the particulate composition is more preferably 5% by weight or less, 3% by weight or less or 1% by weight or less based on the weight of the particulate composition.

In addition to the cyclopropene compound complex, the particles of the particle composition may contain any substance (referred to as "inert" substance) which allows the particle to maintain a solid state and does not inhibit the function of the cyclopropene compound. Substances suitable for inclusion in the particulate composition include, for example, sand (e.g., feldspar sand), clay (e.g., montmorillonite or magnesium aluminum sepiolite), coal powder, broken bricks, cellulosic fibers or other cellulosic materials, polymers. , ground corn cobs, fertilizer or a mixture thereof. Alternatively, the particles of the particulate composition may be coated with, for example, a polymer, graphite, wax, or a combination thereof.

Rice usually grows in rice fields. Rice fields have water in part or all of the plant growth cycle. Rice seeds can be planted in rice fields before the rice fields are released; and in this case, the rice seeds sometimes grow into seedlings before the rice fields are released. Optionally, the rice seed can be planted in a place other than the rice field, and then the seedling is transplanted into the rice field before the rice field is drained. Usually, when the seedlings (grow from rice or transplanted from other places) grow well in the un-watered paddy fields, water can be released in the rice fields. In many cases, rice fields maintain water until they are harvested. Sometimes, rice fields are temporarily drained one or more times during the growth cycle of rice plants. When the rice field has water, the depth of the water is preferably between 20 mm and 100 mm. In a preferred embodiment, the rice fields have water from the time of transplanting to the harvesting.

The rice used in the practice of the present invention may be any species of the genus Oryza . Preferred is cultivated rice ( Oryza sativa L.).

In the practice of the invention, during the growth cycle of the rice plant, The granular composition is applied one or more times in the water of the paddy field. The particulate composition can be applied at any time from transplanting the seedling to harvesting. For a description of the rice growth stage, refer to the BBCH scale for rice (promulgated by the Federal Agricultural and Biological Research Center in Berlin and Braunschweig, Germany), for example at www.jki.bund.de/fileadmin/dam_uploads/_veroeff/ See the BBCH scale at bbch/BBCH-Skala_englisch.pdf. The BBCH scale provides a code number for each step in the rice growth cycle, encoding from 00 (dry seed [Core]) to 99 (product harvested).

Preferably, the rice is treated in one or more of the following growth stages (i.e., the granular composition of the invention is applied in the water of the rice field): ear development (BBCH code 30-32), booting stage (BBCH code 40-45), Initial stage of heading (BBCH code 51-54), after flowering (BBCH code 65-70). In one embodiment, the treatment provided is performed at the booting stage. In another embodiment, the treatment provided is performed in the middle of the booting stage (BBCH code 43).

It is preferred to treat rice exposed to high temperatures at night or high temperatures during the day. It can be treated before, during, and after exposure to high temperatures. It is preferred to treat the rice prior to exposure to high temperatures. This can be achieved by identifying rice that is expected to experience high temperatures, possibly because the rice is growing in a location that typically experiences high temperatures, or because of local weather forecasts.

When the minimum temperature at night is above 23 ° C, it is the night high temperature. The treated rice preferably undergoes one or more nights with a minimum temperature above 23 °C, and the treated rice preferably experiences one or more nights with a minimum temperature above 25 °C. When the high temperature during the day is 32 ° C or more, it is a daytime high temperature. The treated rice preferably experiences one or more of the highest temperature above 32 ° C or Multiple days; the treated rice is better experienced in one or more days with a maximum temperature above 34 °C.

One suitable mode for describing the amount of the cyclopropene compound is the number of grams of the cyclopropene compound (the active ingredient is simply referred to as "ai" or "a.i.") applied per unit area. This amount is expressed in grams of active ingredient per hectare (grams per hectare).

The application rate of the cyclopropene compound of the preferred embodiment is 1 g/ha or more, more preferably 2 g/ha or more, still more preferably 5 g/ha or more. The cyclopropene compound application rate of the preferred embodiment is 100 g/ha or less, more preferably 60 g/ha or less, still more preferably 40 g/ha or less.

Another feature of the treatment method can include a "distribution ratio" of the application of the particles. The particles are believed to be distributed in the rice field in a random but consistent manner. That is, in the case of small areas (for example, 5 cm x 5 cm), the randomness of the particle distribution pattern is considered to be obvious, but the cyclopropene compound is provided in each large area (0.5 m x 0.5 m or more). The quantity is consistent. “Amount of Consistency” means that for the entire paddy field, if the area of 0.5 m x 0.5 m is examined and the amount of cyclopropene compound is measured, the standard deviation of the distribution of these quantities will be an average of 20 %the following.

The analysis of "distribution ratio" refers to the application of standard particles. The standard granules as used in the present application have 0.1% by weight of a cyclopropene compound based on the total weight of the granules. When the standard particles are distributed in a random but consistent manner, the density is set to 100%. To transform the density, an area greater than 0.25 square meters can be divided into several cells each of 0.5 meters x 0.5 meters. Standard particles can be randomly and consistently spread in some communities Within the other cells, no particles are dispersed. The entire region is then referred to as a distribution ratio of D%, where D% = 100 * (number of cells containing particles) / (total number of cells). It is expected that the transformation density can simulate the effect of using particles of different sizes or particles of higher concentration.

The distribution ratio in the examples is preferably 25% or more, more preferably 50% or more, still more preferably 100% or more.

The term "transgenic gene vector" as used in this application refers to a vector containing an inserted DNA fragment which is transcribed into mRNA or replicated into RNA in a host cell. The term "transgenic gene" refers not only to the portion of the inserted DNA that is transcribed into RNA, but also to the portion of the vector required for RNA transcription or replication. A transgenic gene typically comprises a gene of interest, but does not necessarily have to include a polynucleotide sequence containing an open reading frame that produces a protein.

In the practice of the invention, the plant or plant part can be treated. One example treats whole plants; another example treats whole plants grown in the soil before harvesting useful plant parts.

In the practice of the invention, any plant that provides a useful plant part can be treated. Examples include plants that provide fruits, vegetables, and grains.

The term "plant" as used in this application includes dicots and monocots. Examples of dicotyledons include tobacco, arabian mustard, soybean, tomato, papaya, canola, sunflower, cotton, alfalfa, potato, vine, pea, pea, cruciferous, chickpea, beet, rapeseed, watermelon, Melons, green peppers, peanuts, pumpkin, radish, spinach, gourd, broccoli, kale, carrot, broccoli, celery, large Cabbage, cucumber, eggplant, lettuce. Examples of monocots include corn, rice, wheat, sugar cane, barley, rye, sorghum, orchid, bamboo, banana, cattail, lily, oat, onion, millet, and triticale. Examples of fruits include bananas, pineapples, oranges, grapes, grapefruits, watermelons, melons, apples, peaches, pears, kiwis, mangoes, nectarines, guava, persimmons, avocados, lemons, figs, and berries.

The pressing action is a multi-step process in which a strip-shaped pressed product is formed between the rollers applying pressure to the powder to be pressed. The ribbon is then granulated and sieved to the appropriate size. The production of pressed products, such as fertilizers, is usually accomplished by a final processing unit that polishes the particles to improve appearance, reduce the amount of residual fines and facilitate storage. A representative process provided by the present application is shown in FIG.

In one embodiment, the fines produced during the granulation will be completely recovered in the system and re-mixed into the original powder blend. This recycling not only reduces waste, but is also part of the overall process because it does increase the compressibility of the powder and produces stronger particles.

A suitable binder is provided to enhance the particle integrity of the disclosed particle formulation. These suitable binders are selected based on low moisture content and chemical inertness to the active ingredients.

Corn Starch: A dry powdered starch.

Lignosulfonate: Dry powdered sodium lignosulfonate from Borregaard Ligno Tech.

Potassium citrate: The trade name is KASIL ^® SS. Powdered potassium citrate is from PQ Corporation of Valley Forge, Pennsylvania, USA.

Carbowax ^® 8000: Carbowax 8000 is a powdered polyethylene glycol with an average molecular weight of 8800. Its moisture content is less than 0.1%. This product is from Dow Chemical Company.

IGI Wax 1236A: IGI 1236A is a fully refined paraffin having a typical melting point of 55.6 ° C and a specific gravity of 0.91 at 25 ° C. International Group Inc. (IGI) provides commodities in pellet form.

Polyset 2016A: Polyset 2016A is a hard micronized high melting point polyethylene. The softening point is about 117 °C. This product is provided by International Group Limited (IGI).

Feeco clay: The clay used by Feeco is from unmodified sodium bentonite clay from Wyoming. This is a product of Black Hills Bentonite LLC in Wyoming. Its moisture content is 10%. So far, all of our experiments have used this clay. Unfortunately, we know that the clay is no longer available for commercial use.

Volcaly: Volcaly is a naturally occurring sodium bentonite with an average particle size of less than 200 mesh. The maximum humidity at the time of shipment is 12%. The clay is from the American Colloid Company located in Illinois, USA.

Best Bond and Probond 30: Both are activated sodium bentonites. The particle size is 80% or more and passes through 200 mesh. The moisture content is within 14%. It is a product of Volclay Siam (Thailand), and Siken Siam is a wholly-owned subsidiary of AMCOL International.

Pelbon: Pelbon is a high quality calcium bentonite 150 mesh powder is supplied. The maximum moisture content is 15%. The clay is from the American colloid company.

Flue Gas Desulfurization Gypsum: A flue gas desulfurization gypsum is a synthetic calcium sulfate (CaSO ₄ .H ₂ O) product derived from a flue gas desulfurization (FGD) system of a power plant. The product is wet when shipped. The product is manufactured by Headwaters Resources, Inc., West Chester, PA.

CaSO ₄ .H ₂ O: Calcium sulfate (gypsum) may have different degrees of hydration. It is widely used in gypsum board and plaster. Its anhydrate is a powerful desiccant.

KCl: Potassium chloride is also known as potash. This is an extremely common fertilizer. Potassium fertilizer without added iron is also called white potassium fertilizer.

K ₂ SO ₄ : Potassium sulfate is also known as potassium sulfate fertilizer. Potassium sulphate is mainly used as a fertilizer. K ₂ SO ₄ does not contain chlorides, which may be harmful to some crops.

NaCl: Sodium chloride is the main component of sea salt and salt.

B200: B200 is an unmodified corn starch from yellow corn dried by a belt dryer. Its moisture content is at most 11%. It is a product of Grain Processing Company (GPC) from Muscatine, Iowa.

Spress B820: Spress is a pre-gelatinized corn starch for direct compression. The maximum moisture content is 14%. It is a product of GPC.

Pure-Dent B810: Pure-Dent is a multi-functional excipient of corn starch that provides lozenge adhesion, load, lubrication and disintegration. quality. The maximum moisture content is 15%. It is a product of GPC.

Pressing Process: Pressing (or granulating) is a process that expands the size of the powder material into a sheet with or without the use of a binder. The bonding of the material is ensured by the mechanical pressure exerted on the product by the pressing device. The flakes are then crushed and sieved to produce a product in the form of particles of the desired size. The pressing/granulation process can agglomerate a wider variety of materials than other processes (e.g., wet agglomeration) and provide a specified range of product constant sizes. The capacity of the pressing/granulation unit is generally from 50 kg/hr to 100 t/hr. Advantages of compaction include reduced volume, stability of the mixture during processing, elimination of dust problems, control of hardness, recovery of fines, and stability of moisture and/or heat sensitive compounds.

Rolling is a dry granulation process in which many factors need to be considered, controlled and optimized; for example, choice of carrier, choice of dry binder, roll pressure, roll speed and feed of starting materials rate. These factors can determine various properties of the final particulate product (e.g., forming ribbons, etc.). Therefore, important product qualities such as density of the ribbon, flowability, compressibility of the granules, and strength of the finished granules are highly dependent on such factors.

The pressing action is a multi-step process in which a strip-shaped pressed product is formed between the rollers applying pressure to the powder to be pressed. The ribbon is then granulated and sieved to the appropriate size. The production of the pressed product is usually accomplished by a final processing unit which polishes the particles to improve appearance, reduce the amount of residual fines and facilitate storage. A representative press process used is shown in Figure 1.

All of the fines produced during the granulation can be completely recovered in the system and re-mixed into the original powder blend. This recycling not only reduces waste, but is also part of the overall process because it does increase the compressibility of the powder and produces stronger particles.

The stock carrier was dried overnight in a shallow dish in an oven. The temperature used in the pressing process is between 40 ° C and 150 ° C, between 60 ° C and 120 ° C, or between 80 ° C and 100 ° C. The resulting product is screened with a common sieve tray of different sizes to the correct size. In some embodiments, a chemical (inorganic) fertilizer can also act as a carrier.

Skilled artisans will appreciate that there may be some variation based on the disclosure provided. The following examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention or the scope of the claims.

Instance

Preparation of the granule formulation: Unless otherwise explicitly stated in the present application, more than 90% by weight of the granules contained are between 0.1 mm and 10 mm in particle size, based on the weight of the granule formulation.

Assessing crop yield improvement: Each treatment area was compared to an untreated control area. The results are shown as "DY%" (% of yield difference), which is defined as follows: DY% = 100 * [( Y _T - Y _U / Y _U ] where Y _T = yield of the treatment zone, and Y _U = untreated zone For example, when DY is 10%, it means that the yield of the treated area is 10% higher than that of the untreated area. A negative yield difference indicates that the yield of the treated crop is lower than that of the untreated crop.

Example 1 - 1-MCP Stability in the Presence of Carrier

To achieve good field coverage, the volume of the particle formulation is increased by dilution with at least one inert carrier. The carrier was tested using a roller press in the presence of 0.1% 1-MCP equivalent of HAIP (highly active ingredient granules; a powder of 1-MCP complexed with alpha-cyclodextrin). The chemical stability of the blend (before pressing) and the first pass of the material and the recycled material was analyzed.

All carriers were dried overnight at 65 ° C (or 150 ° F) with residual moisture levels close to or below 0.5%, except for bentonite. The average moisture of the bentonite after drying in an oven was about 2.61%. For the sake of clarity, only data from the recovered material is presented in Table 1.

In terms of chemical stability, limestone and bentonite appear to be the best carriers. However, it may be desirable to add an adjuvant to the powders to increase the particle integrity with the carriers, which are currently in a poor to extremely poor state.

Example 2 - Additional Carrier

Three different clays were tested in this example: sodium, calcium and activated bentonite clay. All clays have a very high initial moisture content (from 7% to 13%). Gypsum of varying degrees of hydration was tested: calcined gypsum (dried at 105 ° C) and anhydrite (from Aldrich). Gypsum FGD was dried overnight at 120 °C. The moisture content is shown in Table 2 below. All salts have a very low moisture content (less than 1%). Conversely, corn starch has a relatively high moisture content (about 10%).

The result of drying the clay without increasing stability is unexpected and surprising because HAIP is known to be sensitive to moisture. Result It is shown that if the pressed product contains clay with a certain moisture content, its stability is higher than that of products containing dry clay.

However, some carriers, such as calcined gypsum and anhydrite, can cause severe HAIP degradation regardless of their moisture content. Furthermore, the results show that all dried salts (the moisture content of these dried salts are extremely low) cause significant HAIP degradation.

A long-term study was conducted to confirm the effect of moisture on the stability, and the results are shown in Fig. 2. These results confirm the previously surprising finding that clays with a certain moisture content are beneficial to the chemical stability of the particles.

Another experiment showed that the use of an inert binder had no effect on the stability of the clay due to its moisture content. The stability data for samples with or without cornstarch binder is shown in Figure 3.

Example 3 - Release rate

In a 250 ml glass vial, about 600 mg of a sample containing 0.1% 1-MCP and 120 mg of a sample containing 0.5% 1-MCP were added. Next, 5 ml of Milli Q pure water was added and the bottle was capped. Slightly swirl the bottle to allow the sample to wet and begin to release. Sampling and continuous sampling for 4 hours per hour without further shaking or rotating the sample. After 24 hours, the sample was spun on a rotator for 30 minutes to release any remaining 1-MCP gas and then analyzed again. The results are shown in Figure 4.

As shown in Figure 4, the release of 1-MCP gas from a bentonite sample containing 0.5% 1-MCP (samples O and P) was compared to a sample containing only 0.1% 1-MCP (test Samples L, M, and N) are much faster. Upon contact, water is allowed to penetrate by expanding the clay. When the sodium bentonite clay is wet, It can be expanded to 8 to 10 times its weight. The data shows that the release rate of samples containing more clay and less 1-MCP is slower. In samples containing 0.5% 1-MCP, HAIP contacted water more rapidly, and as the HAIP dissolved, more water penetrated into the particles, creating a number of conduits for gas to escape.

Another experiment showed that the dissolution rate of particles immersed in water was related to 1-MCP%. The results are shown in Figure 5.

Example 4 - Bentonite and Limestone Particle Formulation

Two concentrations of particles (0.1% 1-MCP and 0.5% 1-MCP) were made using a modified rolling process. The advantage of pressing is that no adhesive is used and it is easy to change for large-scale production.

In addition, several carriers and dry binders were tested for the chemical compatibility/stability of HAIP and particle integrity (especially for crushing pressure and abrasion resistance).

Bentonite and limestone show the best overall chemical stability and particle strength. When the chemical stability was tested at 54 ° C for two weeks or longer, the particles showed only minimal degradation. After pressing, when the molecular sieve was added during the formulation, it was surprisingly found that it did not contribute to chemical stability, but unexpectedly adversely affected the particle strength. The results are shown in Table 3.

When a high concentration of bentonite particles (0.5% 1-MCP) was completely immersed in water, it released the active ingredient (1-MCP) within 4 hours without stirring. Low concentrations of bentonite particles (0.1% 1-MCP) released the active ingredient very slowly during 24 hours (1 day) without agitation. The moisture % data after pressing of the particle formulation of limestone and bentonite is shown in Table 4.

Example 5 - Additional Bentonite and Limestone Particle Formulation

The moisture content of bentonite and limestone seems to depend on the stability of the particle formulation. The bentonite was dried to a moisture content of less than 1% by heating at 104 ° C for 24 hours. However, at such a low moisture content, the pressing efficiency of the bentonite becomes not high regardless of the presence or absence of the binder. The addition of molecular sieves unexpectedly has a negative impact on particle integrity. The physical stability of various bentonite and limestone particle formulations was tested and the results are shown in Table 5.

Sodium bentonite and limestone granules were prepared with 5% or 15% micronized polyethylene binder, respectively. All pellets were reprocessed with 50% recycled fines. The data results of compression and abrasion are shown in Table 6 (showing the average of the two sets of data).

Example 6 - Analysis of the upper void sample

In a 607 ml bottle with a sampling port, 100 grams of AGF-B (0.5% 1-MCP particles) of batch B-3 was added. Samples were stored at room temperature (RT), 38 ° C or 50 ° C for six months and periodically sampled. Isobutylene was used as the analytical standard. The data is shown in Table 7.

Immediately after pressing with a roller press, the pellets were placed in a 250 ml narrow-mouth bottle for upper void analysis. Fill the bottle with granules to about 1/3 full and cover with a gas-tight lid with a sampling port. Once the sample is capped, it will not open. The upper void analysis can represent and simulate the flammability of the particle formulation after storage in a cladding or enclosed space.

Even in the worst case (sample stored at 50 ° C), the upper void value is still low, and most of it is below 200 ppm. At 38 ° C and room temperature, the upper voids were mostly below 50 ppm, indicating the stability of the tested particle samples.

Example 7 - Long-term stability test

The HAIP was manually screened to remove the agglomerates. The mesh size is approximately 1 mm or 18 mesh. The screened HAIP is then blended with Vecco clay (American Colloids, Illinois, USA). A gentle mixing was carried out in a half full glass bottle which was spun on a Glas-Col drum (speed of 40% of the highest speed setting) for 10 minutes. Two concentrations of the blend were prepared: 0.5% 1-MCP and 1% 1-MCP. The sample series prepared in this example is shown in Table 8.

After the pressing, the ribbon was placed at room temperature or 54 ° C for about 6 months for stability testing. The pellets of Samples 7-3 and 7-4 (1% 1-MCP, moist clay and no binder) were of good overall quality and chemical stability. After about 6 months, the samples 7-3 and 7-4 made with clay with a moisture content of 10% did not lose more than 3% of the total 1-MCP at room temperature, while the loss at 54 °C was Between 5% and 11% of the total 1-MCP. The stability of other samples made with dry clay is better than Low, its degradation at room temperature is between 3% and 10% of total 1-MCP, and its degradation at 54 °C is between 19% and 23% of total 1-MCP. Most of the degradation occurs during the first week of aging. No significant difference was observed between 0.5% 1-MCP and 1.0% 1-MCP.

The rice plants planted in the open field were treated using the particle formulations of samples 7-3 and 7-4. Typical treatment levels for 1-MCP range from 10 grams of active ingredient (a.i.) per hectare (or 4 grams of active ingredient per acre) to 100 grams of active ingredient per hectare (or 40 grams of active ingredient per acre). The optimal rice growth stage for treatment is from the highest tillering stage to the grain filling stage (for example, at least one of the following: meiosis, full bloom and grain filling). A single 1-MCP treatment is usually performed before harvesting, but a 1-MCP treatment may be performed multiple times before harvesting. The 1-MCP treatment performed on rice plants showed an increase in yield of 14% to 28%, depending on the amount of 1-MCP and the period of treatment. Field test data for a single application of 1-MCP at 50 grams of active ingredient per hectare using sample 7-3 (particle formulation containing 1% 1-MCP) is shown in Table 9.

Claims (25)

A particle formulation comprising: (a) a molecular complex consisting of a volatile compound and a molecular encapsulating agent; and (b) a carrier component having a moisture content of between 5% and 35% . The particle formulation of claim 1 wherein the moisture content is between 7% and 15%. The particle formulation of claim 1 wherein the carrier component comprises clay. The granule formulation of claim 1 wherein the carrier component comprises a combination of bentonite, limestone or the like. The particle formulation of claim 1 wherein the carrier component comprises sodium bentonite clay. The granule formulation of claim 1 wherein the granule formulation does not comprise a binder component. The particle formulation of claim 1 wherein the chemical stability of the molecular complex is improved as compared to a control formulation lacking a carrier component having a moisture content between 5% and 35%. The particle formulation of claim 7, wherein the chemical stability of the molecular complex is increased by at least two fold. The particle formulation of claim 1, wherein the volatile compound comprises a cyclopropene compound of the formula: Wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or naphthyl group; wherein the substituents are independently halogen, alkoxy Or a substituted or unsubstituted phenoxy group. A particle formulation as claimed in claim 9, wherein R is a C _1-8 alkyl group. A particle formulation as claimed in claim 9, wherein R is a methyl group. The particle formulation of claim 1, wherein the volatile compound comprises a cyclopropene compound of the formula: Wherein R ¹ is a substituted or unsubstituted C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkenyl group, a C ₁ -C ₄ alkynyl group, a C ₁ -C ₄ cycloalkyl group, a cycloalkylalkyl group Or phenyl or naphthyl; and R ² , R ³ and R ⁴ are hydrogen. The particle formulation of claim 1 wherein the cyclopropene compound comprises 1-methylcyclopropene (1-MCP). The granule formulation of claim 13, wherein the granule formulation comprises between 0.1% and 10% of 1-MCP. The granule formulation of claim 14, wherein the granule formulation comprises between 0.3% and 3% of 1-MCP. The particle formulation of claim 1, wherein the molecular encapsulating agent is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof. The particle formulation of claim 1, wherein the molecular encapsulating agent comprises an alpha-cyclodide fine. A method of stabilizing a molecular complex consisting of a volatile compound and a molecular encapsulating agent comprising preparing a particulate formulation using a carrier component having a moisture content of between 5% and 35%. A method for preparing a particle formulation according to claim 1, which comprises using a rolling method and a carrier component having a moisture content of between 5% and 35%. The method of claim 19, wherein the rolling method does not use a binder. The method of claim 19, wherein the milling method does not use a molecular sieve. A method of crop yield increase and/or yield protection comprising applying a pellet formulation of claim 1 to a field planting the crop, wherein the crop plant is in a reproductive or maturity phase. The method of claim 22, wherein the crop is selected from the group consisting of rice, corn, wheat, soybean, canola, and cotton. The method of claim 22, wherein the particulate formulation comprises 1-methylcyclopropene (1-MCP). The method of claim 24, wherein the application rate of 1-MCP is between 10 grams of active ingredient per hectare and 100 grams of active ingredient per hectare.