CN105377032A - Methods and compositions of granule formulations - Google Patents
Methods and compositions of granule formulations Download PDFInfo
- Publication number
- CN105377032A CN105377032A CN201480038766.7A CN201480038766A CN105377032A CN 105377032 A CN105377032 A CN 105377032A CN 201480038766 A CN201480038766 A CN 201480038766A CN 105377032 A CN105377032 A CN 105377032A
- Authority
- CN
- China
- Prior art keywords
- granular preparation
- mcp
- group
- alkyl
- moisture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/04—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a three-membered ring
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Cultivation Of Plants (AREA)
- Medicinal Preparation (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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
Background technology
Sometimes need to use compound cyclopropene to promote the growth of crop plants.U.S. Patent Publication 2007/0165166 discloses the method relating to and crop plants is contacted with composition, and described composition comprises compound cyclopropene.In the example of US2007/0165166, described contact is undertaken by being sprayed to by fluid composition on plant.Exist and comprise the relevant shortcoming of the fluid composition of compound cyclopropene with use.Fluid composition needs special installation, such as spraying equipment, and sometimes can not get described equipment.In addition, fluid composition is stored in enclosed slot or other closed container usually.If fluid composition comprises volatility compound cyclopropene, then the head space in closed container can accumulate the VOC of high concentration, and this can produce danger situation.
Also there is shortcoming gas composition being applied to the crop plants in field.When for open wide field in time, gas composition will be diffused in air, may be little or inoperative to it to rice plant action.
Rice is the monocotyledonous seed of Oryza.Term " rice " in the application is used in reference to the rice seed of results or seed growth maybe will the rice plant of growth on it.Two kinds of main rice kinds under cultivation comprise Asian Cultivated Rice (OryzasativaL.) and Oryza glaberrima Steud (OryzaglaberrimaSteud).Rice is important crop plants.Need to provide and use the method for compound cyclopropene, described method promotes the growth of rice and/or other plant, and that avoids in above-mentioned shortcoming is one or more simultaneously.
Summary of the invention
The present invention relates to the granular preparation of molecular complex, described molecular complex comprises volatile compound, wherein in this granular preparation, does not need auxiliary material/binding agent.In addition, the granular preparation surprisingly using molecular sieve that the application is provided is unstable, does not therefore need molecular sieve.Be provided for the method for the granular preparation preparing molecular complex, described molecular complex comprises volatile compound, and providing package is containing the composition of this granular preparation.In addition, the method for compositions-treated plant or the plant part using the application to disclose also is provided.
On the one hand, provide granular preparation, described granular preparation comprises the molecular complex of (a) volatile compound and molecular encapsulation agent; (b) moisture is the carrier component of 5% to 35%.
In one embodiment, moisture is 7% to 15%; Or 8% to 12%.In another embodiment, moisture is at least 10%.In another embodiment, moisture is about 10%.
In another embodiment, described carrier component comprises clay.In another embodiment, described carrier component comprises bentonite, lime stone or its combination.In another embodiment, described carrier component comprises sodium bentonite.In another embodiment, described granular preparation does not comprise binder component.
In another embodiment, and do not have compared with control formulation that moisture is the carrier component of 5% to 35%, the chemical stability of described molecular complex is improved.In a further embodiment, the improved chemical stability at least twice of described molecular complex.In another embodiment, the improved chemical stability twice to five times of described molecular complex.In another embodiment, in room temperature, at 54 DEG C or improve the chemical stability of described molecular complexes room temperature and 54 DEG C.
In another embodiment, described volatile compound comprises the compound cyclopropene of following formula:
Wherein R be replace or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl or naphthyl; Wherein said substituting group is halogen, alkoxyl or replace or unsubstituted phenoxy group independently.In one embodiment, R is C
1-8alkyl.In another embodiment, R is methyl.
In another embodiment, described volatile compound comprises the compound cyclopropene of following formula:
Wherein R
1for that replace or unsubstituted C
1-C
4alkyl, C
1-C
4thiazolinyl, C
1-C
4alkynyl, C
1-C
4cycloalkyl, cycloalkyl-alkyl, phenyl or naphthyl; R
2, R
3and R
4for hydrogen.In another embodiment, described compound cyclopropene comprises 1-methyl cyclopropene (1-MCP).
In another embodiment, granular preparation comprises 0.1% to 10%; 0.3% to 3%; Or the 1-MCP of 0.5% to 1.5%.In another embodiment, described molecular encapsulation agent is selected from alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin or its combination.In another embodiment, described molecular encapsulation agent comprises alpha-cyclodextrin.
On the other hand, provide the method that the molecular complex that makes volatile compound and molecular encapsulation agent is stable, described method comprise use moisture be 5% to 35% carrier component prepare granular preparation.
In one embodiment, moisture is 7% to 15%; Or 8% to 12%.In another embodiment, moisture is at least 10%.In another embodiment, moisture is about 10%.
In another embodiment, described carrier component comprises clay.In another embodiment, described carrier component comprises bentonite, lime stone or its combination.In another embodiment, described carrier component comprises sodium bentonite.In another embodiment, described granular preparation does not comprise binder component.
In another embodiment, and do not have compared with control formulation that moisture is the carrier component of 5% to 35%, the chemical stability of described molecular complex is improved.In a further embodiment, the improved chemical stability at least twice of described molecular complex.In another embodiment, the improved chemical stability twice to five times of described molecular complex.In another embodiment, in room temperature, at 54 DEG C or improve the chemical stability of described molecular complexes room temperature and 54 DEG C.
In another embodiment, described volatile compound comprises the compound cyclopropene of following formula:
Wherein R be replace or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl or naphthyl; Wherein said substituting group is halogen, alkoxyl or replace or unsubstituted phenoxy group independently.In one embodiment, R is C
1-8alkyl.In another embodiment, R is methyl.
In another embodiment, described volatile compound comprises the compound cyclopropene of following formula:
Wherein R
1for that replace or unsubstituted C
1-C
4alkyl, C
1-C
4thiazolinyl, C
1-C
4alkynyl, C
1-C
4cycloalkyl, cycloalkyl-alkyl, phenyl or naphthyl; R
2, R
3and R
4for hydrogen.In another embodiment, described compound cyclopropene comprises 1-methyl cyclopropene (1-MCP).
In another embodiment, granular preparation comprises 0.1% to 10%; 0.3% to 3%; Or the 1-MCP of 0.5% to 1.5%.In another embodiment, described molecular encapsulation agent is selected from alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin or its combination.In another embodiment, described molecular encapsulation agent comprises alpha-cyclodextrin.
On the other hand, the method preparing the granular preparation that the application provides is provided for.Described method comprises the rolling process that use moisture is the carrier component of 5% to 35%.
In one embodiment, binding agent is not used in described rolling process.In another embodiment, molecular sieve is not used in described rolling process.
On the other hand, provide the method that crop plants output increases and/or output is protected, the granular preparation that comprising provides the application is applied to the field of raise crop plant, and wherein said crop plants was in reproduction period or maturing stage.
In one embodiment, crop plants is selected from rice plant, corn plant, wheat plant, bean plant, canola plant and vegetable lamb.In another embodiment, granular preparation comprises 1-methyl cyclopropene (1-MCP).In another embodiment, the rate of application of 1-MCP is that 10g active component (a.i.)/hectare is to 100ga.i./hectare; 20ga.i./hectare is to 70ga.i./hectare; Or 40ga.i./hectare is to 60ga.i./hectare.In another embodiment, the rate of application of 1-MCP is about 50ga.i./hectare.
Accompanying drawing explanation
Fig. 1 display is used for the representative rolling process of the granular preparation that the application provides.
Fig. 2 is presented at the representative result (plot mean) of 54 DEG C of moisture on the impact of degraded.
Fig. 3 shows the representative result (plot mean) of binding agent on the impact of degraded.
Fig. 4 display is from the representative 1-MCP release rate comprising bentonitic preparation.Sample L, M and N comprise 0.1%I-MCP, and sample O and P comprises 0.5%1-MCP.
Fig. 5 shows the representative correlation be immersed in the water between the dissolution rate of particle and 1-MCP%.
Fig. 6 display is from the representative data of the head space of 0.5%1-MCP in sodium bentonite particle.
Embodiment
The present invention is based on following surprising result: the granular preparation of molecular complex does not need auxiliary material/binding agent, and described molecular complex comprises volatile compound.In addition, the granular preparation surprisingly using molecular sieve that the application is provided is unstable, does not therefore need molecular sieve.Be provided for the method for the granular preparation preparing molecular complex, described molecular complex comprises volatile compound, and comprises the composition of this granular preparation.The method of compositions-treated plant or the plant part using the application to disclose also is provided.
The feature of solid particle is the particle diameter of solid particle.If fruit granule is not spherical, then the particle diameter of described particle is regarded as the diameter of the spheroid identical with the volume of described particle at this.
Sometimes need preparation dry state product, avoid using water.Compacting (or granulation) is that particle increases technique, and described technique is at use binding agent or do not use when binding agent dusty material is pressed into sheet.By compacting equipment, the mechanical pressure that product applies is guaranteed to the combination of material.Then sheet is broken and screening, the product of the required size of preparation particle form.
Substituting as wet method agglomeration, compacting/prilling allows the agglomeration of relative broad range material than other technique, and provides specific and constant product size scope.The ability of compacting/Granulation Equipments typically is 50Kg/h to 100T/h.
Roll-in is dry granulation method, wherein needs to consider, control and the many factors of optimization; Such as, the rate of feed of carrier and binding agent, roll-in, roller speed and raw material is selected.These factor determination product properties (being such as with formation) and final particle properties.Important product quality such as with density, the mobility of particle, compressibility, and final granule strength, highly depend on above-mentioned parameter.
It is important for controlling the product of these factors to the required quality of realization.Fully understand that the chemical property of raw material and physical property and technological parameter are also necessary.Many goods can be obtained by compaction process.But, most of agricultural application restriction fertilizer formulations.
Except as otherwise noted, following term used has definition given below otherwise in the application's (comprising specification and claims).Must be noted that, as used in the specification and the appended claims, unless clearly indicated in addition in context, otherwise singulative comprises plural thing.The definition of standard chemistry terms can obtain in below with reference to works: comprise CareyandSundberg, AdvancedOrganicChemistry the 4th edition, Vols.A (2000) and B (2001), PlenumPress, NewYork, N.Y..
Phrase " group " used in the application refers to specific fragment or the functional group of a molecule.Chemical group is often the chemical entities of the accreditation embedding in molecule or overhang molecule.
Phrase " alkyl " used in the application refers to alkyl that is unsubstituted or that replace, and can comprise linear, branching, ring-type, saturated and/or unsaturated feature.Although alkyl can be " unsaturated alkyl " group, this means that it comprises at least one alkenyl or alkynyl group, typically, alkyl is " saturated alkyl " group, this means that it does not comprise any alkenyl or alkynyl group.Equally, although alkyl can be ring-type, alkyl typically is non-cyclic groups.Therefore, in some embodiments, " alkyl " refers in some embodiments, there is about one to the straight chain of the optional replacement of about 30 carbon atoms or the optional branched-chain saturated hydrocarbon monoradical replaced, in some embodiments, for about one to about 15 carbon atom, with in further embodiment, for about one to about six carbon atom.The example of saturated alkyl group includes but not limited to, methyl, ethyl, n-pro-pyl, isopropyl, 2-methyl isophthalic acid-propyl group, 2-methyl-2-propyl, 2-methyl-1-butene base, 3-methyl isophthalic acid-butyl, 2-methyl-3-butyl, 2, 2-dimethyl-1-propyl group, 2-methyl-1-pentene base, 3-methyl-1-pentene base, 4-methyl-1-pentene base, 2-methyl-2-amyl group, 3-methyl-2-amyl group, 4-methyl-2-amyl group, 2, 2-dimethyl-1-butyl, 3, 3-dimethyl-1-butyl, 2-ethyl-1-butyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, and n-hexyl, longer alkyl, as heptyl and octyl group.It should be noted that when it occurs in this application, number range refers to each integer in given range as " 1 to 6 "; Such as, " 1 to 6 carbon atom " or " C
1-6" or " C
1-C
6" mean that alkyl can comprise 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, and/or 6 carbon atoms, but this definition also covers the situation existing and wherein do not specify the term " alkyl " of number range.
Phrase " substituted alkyl " used in the application refers to the alkyl defined in the application, and wherein one or more (about five at the most, preferably at the most about three) hydrogen atoms are substituted by the substituting group being independently selected from the substituted radical defined in the application.
Phrase " substituting group " used in the application and " replacement " refer to the group that may be used for another group on alternative molecule.This group is that the technical staff in chemical field is known, and can include but not limited to, the group of one or more following independent selections or its subset of specifying: halogen ,-CN ,-OH ,-NO
2,-N
3,=O ,=S ,=NH ,-SO
2,-NH
2,-COOH ,-S (O
2), 4-nitro alkyl, amino, comprise monosubstituted and dibasic amino, cyanato-, isocyanide acyl, sulfo-cyanato-, different sulfo-cyanato-, guanidine radicals (guanidinyl), O-carbamyl, N-carbamyl, thiocarbamoyl, urea groups, isourea base, ghiourea group, isothiourea group, sulfydryl, sulfonyl (sulfanyl), sulfinyl, sulfonyl (sulfonyl), sulfoamido (sulfonamidyl), phosphoryl (phosphonyl), phosphatidyl, phosphinylidyne amido (phosphoramidyl), dialkyl amido, ammonia diaryl base, two aryl alkyl aminos, and the compound protected.The known blocking group that can form above substituent protected compound of those skilled in the art, it can obtain in such as below with reference to document: Greene and Wuts, ProtectiveGroupsinOrganicSynthesis, the third edition; JohnWiley & Sons, NewYork, N.Y. (1999), and Kocienski, ProtectiveGroups; ThiemeVerlag, NewYork, N.Y. (1994), be incorporated in the application by its full content, with for referencial use.
Phrase " alkoxyl " used in the application refers to radical-O-alkyl, and wherein alkyl is by being defined in the application.In one embodiment, alkoxyl comprises, such as, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentyloxy, just own oxygen base, and 1,2-dimethyl butoxy etc.Alkoxyl can be unsubstituted or replacement.
Phrase " ring-type " used in the application and " a few ring " refer to any circulus, comprise alicyclic ring, heterocycle, aromatics, heteroaromatic, and many rings condense or non-condensed member ring systems, as described in this application.Term " a few unit " means the skeletal atom number representing and form ring.Therefore, such as, pyridine, pyrans, and pyrimidine is hexatomic ring; Pyrroles, oxolane, and thiophene is five-membered ring.
Phrase " aromatics " used in the application refers to the ring-type or polycyclic groups with conjugation unsaturated (4n+2) pi-electron system (wherein n is positive integer) (being sometimes called delocalizedπelectron system).
Phrase " aryl " used in the application refers to optional replacement, aromatics ring-type, hydrocarbon monoradical, it has six to about 12 annular atomses, preferably six to about ten carbon atoms, comprise and condense (fused) (or condensing (condensed)) and non-condensed aromatic rings.Fused aromatic cyclic group comprises two to four fused rings, and the ring wherein connected is aromatic ring, and other the single ring in fused rings can be cycloalkyl, cycloalkenyl group, cycloalkynyl radical, Heterocyclylalkyl, heterocycloalkenyl, heterocycle alkynyl, aromatics, heteroaromatic, or its any combination.The nonlimiting examples of single cyclophane base comprises phenyl; Fused rings aryl, comprises naphthyl, anthryl, Azulene base; With non-condensed diaryl, comprise xenyl.
Phrase " substituted aryl " used in the application refers to aryl, as in the application define, wherein one or more (about five at the most, preferably about three at the most) hydrogen atom substitutes by substituting group, and described substituting group independently is selected from the group (beyond the group that the definition of aryl substituent limits unless otherwise) defined in the application.
Phrase " heteroaryl " used in the application refers to optional replacement, aromatics ring-type monoradical, comprise about five to about 12 backbone ring atoms, preferably five to about ten annular atomses, and comprise and condense (fused) (or condensing (condensed)) and non-condensed aromatic rings, and there is one or more (one to ten, preferably about one to about four) annular atoms, described annular atoms is selected from the atom (that is, hetero atom) beyond de-carbon, such as oxygen, nitrogen, sulphur, selenium, phosphorus or its combination.Term heteroaryl comprises condensing and non-condensed heteroaryl groups of optional replacement, and it has at least one hetero atom.Fused heteroaryl group can comprise two to four fused rings, and the ring wherein connected is heteroaromatic rings, and other the single ring in fused ring system can be alicyclic ring, heterocycle, aromatics, heteroaromatic, or its any combination.Term heteroaryl also comprises and has five to the condensing and non-condensed heteroaryl of about 12 backbone ring atoms, and has five to those of about ten backbone ring atoms.The example of heteroaryl includes but not limited to, acridinyl, benzo [1, 3] dioxolen, benzimidazolyl, benzo indazolyl, benzoisoxazole base, benzokisazolyl, benzofuranyl, benzofuraxan base (furazanyl), benzopyranyl, diazosulfide base, benzothiazolyl, benzo [b] thienyl, aisaa benzothiophenyl, benzothiopyran derivative base, BTA base, benzoxazolyl, carbazyl, carboline base, benzopyranyl (chromenyl), cinnolines base (cinnolinyl), furyl, furazan base (furazanyl), furopyridyl (furopyridinyl), furyl, imidazole radicals, indazolyl, indyl, indolyl (indolidinyl), indolizine base (indolizinyl), isobenzofuran-base, isoindolyl, isoxazolyl, isoquinolyl, isothiazolyl, hydrogenation naphthyl (naphthylidinyl), naphthyridines base (naphthyridinyl), oxadiazolyl, oxazolyl, phenoxazine group (phenoxazinyl), phenothiazinyl (phenothiazinyl), phenazinyl (phenazinyl), phenoxathiynyl, thianthrene group (thianthrenyl), phenanthridinyl, phenanthrolene base (phenathrolinyl), 2, 3-phthalazinyl (phthalazinyl), pteridyl (pteridinyl), purine radicals (purinyl), puteridinyl, pyrazolyl (pyrazyl), pyrazolyl (pyrazolyl), pyridine radicals (pyridyl), pyridine radicals (pyridinyl), pyridazinyl (pyridazinyl), pyrazinyl, pyrimidine radicals (pyrimidinyl), pyrimidine radicals (pyrimidyl), pyrrole radicals, quinazolyl, quinolyl (quinolinyl), quinoxalinyl, tetrazole radical, thiadiazolyl group, thiazolyl, thienyl, triazinyl, (1, 2, 3, )-and (1, 2, 4)-triazolyl etc., and oxide time suitably, such as pyridinyl-N-oxide.
Phrase " substituted heteroaryl " used in the application refers to heteroaryl, as in the application define, wherein one or more (about five at the most, preferably at the most about three) hydrogen atoms are substituted by substituting group, and described substituting group is independently selected from the group defined in the application.
Phrase " leaving group " used in the application refers to the group with conventional implication be associated in synthetic organic chemistry with it, that is, alternative under substitution reaction condition atom or group.The example of leaving group includes but not limited to; halogen, alkane-or arylenesulfonyloxy, as methanesulfonyloxy group, ethanesulfonyl oxygen base; sulphomethyl; benzenesulfonyl oxygen base, tosyloxy, and thiophene oxy; dihalo phosphonato (dihalophosphinoyloxy); the benzyloxy of optional replacement, isopropoxy, and acyloxy etc.In some embodiments, leaving group can be HC (O)-COOH or RC (O)-COOH, and wherein R is C
1-C
6the C of alkyl or replacement
1-C
6alkyl.
The compounds of this invention described in the application can use Standard synthetic techniques well known by persons skilled in the art or use the combination of the method described in method as known in the art and the application to synthesize.Raw material for the synthesis of the compounds of this invention described in the application can derive from commercial source, as AldrichChemicalCo. (Milwaukee, Wis.), and SigmaChemicalCo. (St.Louis, Mo.), or can synthesis material.Compound described in the application, technology well known by persons skilled in the art and materials synthesis can be used with other related compound with different substituents, described in such as: March, AdvancedOrganicChemistry the 4th edition (1992) JohnWiley & Sons, NewYork, N.Y.; Carey and Sundberg, AdvancedOrganicChemistry the 4th edition, Vols.A (2000) and B (2001) PlenumPress, NewYork, N.Y., and Greene and Wuts, ProtectiveGroupsinOrganicSynthesis, the third edition (1999) JohnWiley & Sons, NewYork, N.Y. (its full content is incorporated to for referencial use).Usual method for the preparation of compound described in the application can be derived from the known response in this area, and described reaction can by using suitable reagent and condition amendment, as one skilled in the art would realize, for introducing the various groups obtained in the formula that provides in the application.Such as, the compound described in the application can use various electrophilic reagent or nucleopilic reagent amendment to form new functional group or substituting group.
Enforcement the present invention relates to and uses one or more of compound cyclopropene.As used in this application, compound cyclopropene is any compound with following formula
Wherein R
1, R
2, R
3and R
4be selected from the chemical group of H and following formula independently of one another:
-(L)
n-Z
Wherein n is the integer of 0 to 12.Each L is divalent group.Suitable L group comprises such as, comprises one or morely to be selected from H, the group of the atom of B, C, N, O, P, S, Si or its mixture.Atom in L group can pass through singly-bound, double bond, and triple bond or its mixing key are interconnected.Each L group can be linear, branching, ring-type or its combination.At any one R group (i.e. R
1, R
2, R
3and R
4in any one) in, the hetero atom atom of H and C (that is, be not) add up to 0 to 6.Independently, in any one R group, non-hydrogen atom adds up to 50 or less.Each Z is monoradical.Each Z is independently selected from: hydrogen, halogen, cyano group, nitro, nitroso, azido, chlorate anions, bromate, iodate, isocyanide acyl, isonitrile base (isocyanido), different sulfo-cyanato-, five fluorine sulfo-s (pentafluorothio), with chemical group G, wherein G be 3 yuan to 14 ring system.
R
1, R
2, R
3, and R
4group is independently selected from suitable group.Be suitable for and make R
1, R
2, R
3, and R
4in one or more group especially such as, aliphatic group, aliphatic series-oxygen base; alkylphosphines acid group (alkylphosphonato) group, cycloaliphatic groups, naphthene sulfamide base; cycloalkyl amino; heterocyclic group, aryl, heteroaryl; halogen; silicyl, other group, and its mixture and combination.Be suitable for and make R
1, R
2, R
3, and R
4in one or more groups can be replace or unsubstituted.
Suitable R
1, R
2, R
3, and R
4group is aliphatic group especially such as.Some suitable aliphatic groups comprise such as, alkyl, thiazolinyl, and alkynyl group.Suitable aliphatic group can be linear, branching, ring-type or its combination.Independently, suitable aliphatic group can be replacement or unsubstituted.
If one or more hydrogen atoms of object chemical group are substituted by substituting group, then think that object chemical group used is " replacement " in the application.
Suitable R
1, R
2, R
3, and R
4group also especially such as replaces and unsubstituted heterocyclic group, and it is by the oxygen base of insertion, and amino, carbonyl or sulfonyl are connected to compound cyclopropene; This R
1, R
2, R
3, and R
4the example of group is heterocyclic oxy group, heterocyclecarbonyl, two heterocyclic amino group, and two heterocyclic amino group sulfonyls.
Suitable R
1, R
2, R
3, and R
4group also especially such as replaces and unsubstituted heterocyclic group, and it is amino by the oxygen base of insertion, carbonyl, sulfonyl, and alkylthio or amino-sulfonyl are connected to compound cyclopropene; This R
1, R
2, R
3, and R
4the example of group is two heteroaryl aminos, Heteroarylthio alkyl, and two heteroarylaminosulfonyl.
Suitable R
1, R
2, R
3, and R
4group also especially such as, hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, nitroso, azido, chlorate anions, bromate, iodate, isocyanide acyl, isonitrile base, different sulfo-cyanato-, five fluorine sulfo-s; Acetoxyl group, carbethoxyl group (carboethoxy), cyanato-, nitrato, nitrito-, perchlorate (perchlorato), allene base (allenyl), butyl sulfydryl, diethyl phosphonate radical, dimethylphenylsilyl, isoquinolyl, sulfydryl, naphthyl, phenoxy group, phenyl, piperidyl, pyridine radicals, quinolyl, triethylsilyl, trimethyl silyl, and replace analog.
Chemical group G used in the application be 3 yuan to 14 ring system.The suitable member ring systems as chemical group G can be replacement or unsubstituted; They can be aromatics (comprising, such as phenyl and naphthyl) or aliphatic series (comprising unsaturated aliphatic, fractional saturation aliphatic series or radical of saturated aliphatic); Can be carbocyclic ring type or heterocyclic type with them.In heterocycle G group, some suitable hetero atoms such as, nitrogen, sulphur, oxygen, and combination.The suitable member ring systems as chemical group G can be monocycle, dicyclo, three rings, many rings, volution or fused rings; As dicyclo, in the suitable chemical group G member ring systems of three rings or fused rings, each ring in single chemical group G can be all identical type, can be maybe two or more types (such as, aromatic ring can condense with aliphatic ring).
In one embodiment, R
1, R
2, R
3, and R
4in one or more be hydrogen or (C
1-C
10) alkyl.In another embodiment, R
1, R
2, R
3, and R
4be hydrogen or (C separately
1-C
8) alkyl.In another embodiment, R
1, R
2, R
3, and R
4be hydrogen or (C separately
1-C
4) alkyl.In another embodiment, R
1, R
2, R
3, and R
4be hydrogen or methyl separately.In another embodiment, R
1for (C
1-C
4) alkyl, R
2, R
3, and R
4be hydrogen separately.In another embodiment, R
1for methyl, R
2, R
3, and R
4be hydrogen separately, and compound cyclopropene is called 1-methyl cyclopropene or " 1-MCP " in this application.
In another embodiment, described compound cyclopropene has following formula:
Wherein R is substituted or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl, or naphthyl; Wherein said substituting group is halogen independently, alkoxyl, or substituted or unsubstituted phenoxy group.In one embodiment, R is C
1-8alkyl.In another embodiment, R is methyl.
In another embodiment, described compound cyclopropene has following formula:
Wherein R
1for substituted or unsubstituted C
1-C
4alkyl, C
1-C
4thiazolinyl, C
1-C
4alkynyl, C
1-C
4cycloalkyl, cycloalkyl-alkyl, phenyl, or naphthyl; R
2, R
3, and R
4for hydrogen.In another embodiment, described compound cyclopropene comprises 1-methyl cyclopropene (1-MCP).
Preferred following embodiment: being wherein used in an atmospheric boiling point is 50 DEG C or lower; More preferably 25 DEG C or lower; More preferably 15 DEG C or lower compound cyclopropene.Independently, preferred following embodiment: be wherein used in an atmospheric boiling point and be-100 DEG C or higher; More preferably-50 DEG C or higher; More preferably-25 DEG C or higher; More preferably 0 DEG C or higher compound cyclopropene.
Composition of the present invention comprises at least one molecular encapsulation agent, and described at least one molecule encapsulation agent encapsulates the part in one or more compound cyclopropenes or one or more compound cyclopropenes.Comprise the molecular complex being encapsulated in compound cyclopropene molecule in molecule molecular encapsulation agent or a part of compound cyclopropene molecule to be called in this application " compound cyclopropene compound ".
In a preferred embodiment, there is at least one compound cyclopropene compound as inclusion complex.In this kind of inclusion complex, molecule encapsulation agent forms cavity, and compound cyclopropene or a part of compound cyclopropene are positioned at described cavity.
Preferably, in this inclusion complex, the cavity inside of molecule encapsulation agent is essentially nonpolar or hydrophobicity or nonpolar and hydrophobicity, and compound cyclopropene (or being positioned at a part of compound cyclopropene of described cavity) is also essentially nonpolar or hydrophobicity or nonpolar and hydrophobicity.Although the invention is not restricted to any concrete theory or mechanism, but consider in this nonpolar compound cyclopropene compound, Van der Waals force or hydrophobic effect or Van der Waals force and hydrophobic effect impel compound cyclopropene molecule or its part plenty of time to be retained in the cavity of molecule encapsulation agent.
The feature of molecule encapsulation agent spendable amount is, the ratio of the molecule encapsulation molal quantity of agent and the molal quantity of compound cyclopropene.In a preferred embodiment, the molecule encapsulation molal quantity of agent is 0.1 or larger with the ratio of the molal quantity of compound cyclopropene; More preferably 0.2 or larger; More preferably 0.5 or larger; More preferably 0.9 or larger.Independently, in a preferred embodiment, the molecule encapsulation molal quantity of agent is 10 or lower with the ratio of the molal quantity of compound cyclopropene; More preferably 5 or lower; More preferably 2 or lower; More preferably 1.5 or lower.
Suitable molecule encapsulation agent comprises such as, organic and inorganic molecule encapsulation agent.Preferred organic molecule encapsulation agent, it comprises such as, the cyclodextrin of replacement, unsubstituted cyclodextrin, and crown ether.Suitable inorganic molecule encapsulation agent comprises such as, zeolite.Suitable molecule encapsulation agent composition is also suitable.In a preferred embodiment, described molecule encapsulation agent is alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, or its combination.In the preferred embodiment of the present invention, use alpha-cyclodextrin.
Enforcement the present invention relates to use particulate composition.Particulate composition is the composition existed as solid particle under 1 atmospheric pressure with all temperature of 5 DEG C to 40 DEG C.Particulate composition is the aggregate of solid particle, and wherein the aggregate of weight of 90% or more is present in particle diameter is in 1 micron or larger particle, and wherein the aggregate of weight of 90% or more is present in particle diameter is in 5 centimetres or less particle.Preferably wherein the aggregate of weight of 90% or more is present in particle diameter is composition in 10 microns or larger particle.Also preferably wherein the aggregate of weight of 90% or more is present in particle diameter is composition in 1 centimetre or less particle.
In another aspect of this invention, the method improving the cultivation of rice in paddy field is provided, described method comprises in the water be added into by particulate composition in described paddy field, and wherein said particulate composition comprises one or more compound cyclopropenes be encapsulated in molecular encapsulation agent.
Preferred particulate composition comprises the compound cyclopropene of 0.02wt% or more, based on the weight of particulate composition.In preferred particulate composition, the content of compound cyclopropene is 0.05wt% or more based on the weight of particulate composition; Be more preferably 0.09wt% or more.In preferred particulate composition, the content of compound cyclopropene is 5wt% or less based on the weight of particulate composition.In preferred particulate composition, the content of compound cyclopropene is 5wt% or less based on the weight of particulate composition; 3wt% or less; Or 1wt% or less.
Except compound cyclopropene compound, the particle of particulate composition can also comprise permission particle and keeps solid and can not suppress any material of compound cyclopropene function (being called 'inertia' material).The suitable substance be included in particulate composition comprises such as, sand (such as, feldspathic sand), and clay (such as, montmorillonite or attapulgite), coal dust, cracked brick, cellulose fiber or other cellulosic material, polymer, grinds maize cob, fertilizer, or its mixture.Particulate composition particle can optionally such as with polymer, graphite, wax or its combination coating.
Rice often grows in paddy field.Paddy field is the field being all in waterflooding state at certain plants growth cycle or whole plant growing cycle.Before the waterflooding of paddy field, rice can be planted in paddy field, described situation some in, before the waterflooding of paddy field, rice can grow and become seedling.Or rice can for being planted in outside paddy field somewhere, then before the waterflooding of paddy field as sprigging in paddy field.Usually, after seedling grows up in the paddy field of non-waterflooding (by from seed growth or transplanting), then paddy field waterflooding.In many cases, paddy field keeps waterflooding state until gather in the crops not long ago.During plant growing cycle, one or more short-term draining is carried out in paddy field sometimes.When paddy field waterflooding, the degree of depth of water is preferably 20mm to 100mm.In a preferred embodiment, paddy field is from sprigging until gather in the crops the time exceeding half to be in waterflooding state.
For implementing the Oryza that rice of the present invention can be any kind.Preferred Asian Cultivated Rice (OryzasativaL.).
When implementing of the present invention, during plant growing cycle, particulate composition one or many is added in the water in paddy field.From sprigging until during any time of results, can interpolation particulate composition be carried out.Breeding time of rice can by reference to the BBCH classification of rice (by theFederalBiologicalResearchCentreforAgricultureandFores try, BerlinandBraunschweig, Germany publishes) describe, it can such as be consulted by worldwide website jki.bund.de/fileadmin/dam_uploads/_veroeff/bbch/BBCH-Ska la_englisch.pdf..BBCH classification provides the coded number of each step in rice growth cycle, from coding 00 (dry seeds [caryopsis]) to 99 (harvested products).
Preferably during one or more following breeding times, process rice (that is, being added in the water in paddy field by particulate composition of the present invention): fringe grows (BBCH encode 30-32); Booting (BBCH encode 40-45); Early fringe (EarlyHeading) (BBCH encode 51-54); After spending (BBCH encode 65-70).In one embodiment, provided process is carried out between booting stage.In another embodiment, mid-term is carried out provided process (BBCH coding 43) in booting.
Preferred process exposes the rice of paramount nocturnal temperature or high daytime temperature.Before being exposed to high temperature, period or can process afterwards.Preferably be exposed to the pre-treatment rice of high temperature.This is by identifying that expection is exposed to the rice realization of high temperature, because often experiencing position growth or because the specific Local Weather Report of high temperature.
High nocturnal temperature appears at night, and wherein the minimum temperature at this night is 23 DEG C or higher.Preferred process experience minimum temperature at night is the rice at one or more nights of 23 DEG C or higher; More preferably process experience minimum temperature at night is the rice at one or more nights of 25 DEG C or higher.High daytime temperature appears in the daytime, and wherein daytime high temperature is 32 DEG C or higher.Preferred process experience in the daytime maximum temperature more than 32 DEG C or higher one or more rice in the daytime; More preferably one or more rice in the daytime that maximum temperature is in the daytime 34 DEG C or higher are experienced in process.
The useful mode characterizing compound cyclopropene usage amount is illustrate that per unit area uses the grams of compound cyclopropene (active component is abbreviated as " ai " or " a.i. ").Described amount is reported as the grams (g/ha) of per hectare ai.
Preferred embodiment the rate of application of middle compound cyclopropene is 1g/ha or higher; Be more preferably 2g/ha or higher; Be more preferably 5g/ha or higher.Preferred embodiment the rate of application of compound cyclopropene is 100g/ha or lower; Be more preferably 60g/ha or lower; Be more preferably 40g/ha or lower.
Another characteristic of processing method can comprise " distribution score " that particle is used.Think that particle at random but be as one man distributed in rice field.That is, if think that particle checks with small size (such as, 5cm × 5cm) then allow randomness obviously and provide the compound cyclopropene of consistent amount to distribute to the mode of each large area (0.5 meter × 0.5 meter or larger)." unanimously measure " refers in whole rice field, is eachly of a size of the square of 0.5 meter × 0.5 meter if checked and measures the compound cyclopropene of described amount, then the standard deviation of this tittle distribution can be average magnitude 20% or less.
The feature of " distribution score " is with reference to using standard particle.As used in this application, standard particle has the compound cyclopropene of 0.1wt%, based on the gross weight of particle.When standard particle at random but when as one man distributing, think that density is 100%.For a change density, the plot being greater than 0.25 square metre can be divided into is respectively the sub-plot of 0.5 meter × 0.5 meter.Can by standard particle at random but be as one man dispersed in an a little plot, and in other sub-plot not dispersed particulates.Then think that whole plot is that D% scatters with distribution score, wherein D%=100* (comprising the sub-plot number of particle)/(total sub-plot number).Consider that changing density can simulate and use the particle of different size or the effect of more concentrated granular.
Preferred embodiment, distribution score is 25% or higher; Be more preferably 50% or higher; Be more preferably 100% or higher.
As used in this application, phrase " transgene receptor " refers to the acceptor comprising DNA Insert Fragment, and " transgenosis " is transcribed into mRNA or copies as the RNA in host cell.Phrase " transgenosis " not only refers to the described part of the insertion DNA converting RNA to, and refers to and need to transcribe or those parts of carrier of replicated rna.Transgenosis typically comprises genes of interest but need not comprise polynucleotide sequence, and described polynucleotide sequence comprises can produce protedogenous open reading frame.
Plant or plant part can be processed when implementing of the present invention.An example is the whole plant of process; Another example be the useful plant part of results the whole plant of pre-treatment simultaneously by whole planting in soil.
Any plant of the plant part provided can be processed when implementing of the present invention.Example comprises the plant providing fruit, vegetables and cereal.
As used in this application, phrase " plant " comprises dicotyledon and monocotyledon.The example of dicotyledon comprises tobacco, arabidopsis, soybean, tomato, pawpaw, canola, sunflower, cotton, clover, potato, grape vine, pigeon eggs shape beans, pea, mustard genus, chickpea, beet, rape, watermelon, muskmelon, capsicum, peanut, pumpkin, radish, spinach, winter squash, broccoli, wild cabbage, carrot, cauliflower, celery, Chinese cabbage, cucumber, eggplant and romaine lettuce.Monocotyledonous example comprises corn, rice, wheat, sugarcane, barley, rye, Chinese sorghum, orchid, bamboo, banana, cattail, lily, oat, onion, millet and triticale.The example of fruit comprises banana, pineapple, orange, grape, grapefruit, watermelon, muskmelon, apple, peach, pears, kiwi fruit, mango, nectarine, guava, persimmon, avocado, lemon, fig and berry.
Compacting is multi-step process, forms product compaction bar between the wheel wherein applying pressure to compacting on powder.Then by bar granulation and screening to appropriate size.Prepare product compaction (such as fertilizer) to complete frequently by finishing unit, wherein polishing particles is to improve outward appearance, residual fine powder amount minimizing, to be easier to store.The representative processes that the application provides is shown in Figure 1.
In one embodiment, the fine powder produced between granulation stage is fully recycled in system, and mixes again with starting powder blend.Described recycle not only cuts the waste but also is an inalienable part of technique, because its really strengthens the compaction capacity of powder and produces the larger particle of intensity.
There is provided suitable binding agent to increase the granule integrity of disclosed granular preparation.These suitable binding agents are selected with relative activity Components Chemical inertia based on moisture is low.
Corn starch: dry powder-shaped starch.
Lignosulfonates: dry powder sodium lignin sulfonate, derives from BorregaardLignoTech.
Silicon potash fertilizer: with trade name
sS provides.Powder silicon potash fertilizer derives from PQCorporation, ValleyForge, PAUSA.
8000: if the mean molecule quantity of powder polyethylene glycol is 8800, be Carbowax8000.Water content is less than 0.1%.Described product derives from TheDowChemicalCompany.
IGIwax1236A:IGI1236A is paraffin wax fully refined, and its typical fusing point is 55.6 DEG C, is 0.91 at the proportions of 25 DEG C.Thered is provided in granular form by InternationalGroupInc. (IGI).
Polyset2016A:Polyset2016A is hard particulate refractory polyethylene.Softening point is about 117 DEG C.Described product is provided by InternationalGroupInc. (IGI).
FeecoClay:Feeco clay used is constant Wyoming sodium bentonite.It is the product B lackHills bentonite of the LLC being positioned at WY.Moisture is 10%.This is that we are up to now for the clay of our experiments all.Regrettably, we know that described clay at present no longer can measuring with business.
Volclay:Volclay powder is naturally occurring sodium bentonite, and wherein particle mean size is less than 200 orders.Maximal humidity during shipment is 12%.Described clay derives from the AmericanColloidCompany being positioned at IL.
BestBondandProbond30: the two is all activation sodium bentonite.The particle that granularity is at least 80% is sieved by 200 objects.Moisture is 14% to the maximum.They are products of VolclaySiam (Thailand), and VolclaySiam is the wholly-owned subsidiary of AMCOLInternationalCompany.
Pelbon:Pelbon is the calcium bentonite of high-quality, is supplied as 150 object powder.Maximum moisture is 15%.Described clay derives from AmericanColloidCompany.
Gypsum FGD: gypsum FGD is synthesis calcium sulphate (CASO
4.H
2o) product, is derived from flue gas desulfurization (FGD) system in power plant.Described product is wet type shipment.It derives to be positioned at WestChester, the product of the HeadwatersResources of PA.
CaSO
4.H
2o: calcium sulphate (Gypsum) can have different hydrautures.It is widely used in dry wall and gypsum.Dehydrate is strong desiccant.
KCl: potassium chloride (Potassiumchloride) is also referred to as potassium chloride (muriateofpotash).It is the non-fertilizer usually seen.Do not add the described chloride of iron also referred to as white potassium (whitepotash).
K
2sO
4: potassium sulfate (Potassiumsulfate) is also referred to as potassium sulfate (sulfateofpotash).The main application of potassium sulfate is as fertilizer, K
2sO
4do not comprise chloride, it can be harmful to some crops.
NaCl: sodium chloride is the key component of sea salt and salt.
B200:B200 is unmodified corn starch, derives from dry on belt dryer yellow maize.It comprises 11% moisture at the most.This derives to be positioned at Muscatine, the product of the GrainProcessingCompany (GPC) of IA.
SpressB820:Spress is the pre-gelatinized corn starch of direct tablet compressing.Maximum moisture is 14%.This is the product deriving from GPC.
Pure-DentB810:Pure-Dent is corn starch, as multi-functional medium, is supplied to sheet to combine, to carry, to lubricate and disintegrating property.Maximum moisture is 15%.This is the product deriving from GPC.
Compaction process: compacting (or granulation) is that particle increases technique, and described technique is in use or do not use when binding agent dusty material is pressed into sheet material.By compacting equipment, the mechanical pressure that product applies is guaranteed to the combination of material.Then sheet is broken and screening, the product of the required size of preparation particle form.Compacting/prilling can allow the agglomeration (such as wet method agglomeration) of relative broad range material than other technique, and provides specific and constant product size scope.The ability of compacting/Granulation Equipments typically is 50Kg/h to 100T/h.The advantage of compacting comprises volume and reduces, and stabilized with mixture during process, eliminates dust problem, controls hardness, recycle fine powder, and humidity and/or heat sensitive compounds are stablized.
Roll-in is dry granulation method, wherein considers, controls and/or the many factors of optimization; Such as, select carrier, select dry binder, roll-in, roller speed and feedstock rate.These factors can determine the multiple character (such as band is formed) of final grain products.Therefore, important product quality such as with density, the mobility of particle, compressibility, and final granule strength height depends on these factors.
Compacting is multi-step process, forms product compaction bar between the wheel wherein applying pressure to compacting on powder.Then by bar granulation and screening to appropriate size.Prepare product compaction to complete frequently by finishing unit, wherein polishing particles is to improve outward appearance, residual fine powder amount minimizing, to be easier to store.Representative compaction process used is described in Fig. 1.
The whole fine powder produced between granulation stage can be recycled in system, and mixes with starting powder blend again.Described recycle not only cuts the waste but also is an inalienable part of technique, because its really strengthens the compaction capacity of powder and produces the larger particle of intensity.
Raw material carrier spends the night at flat baking oven inner drying.Temperature in compaction process used is 40 DEG C to 150 DEG C; 60 DEG C to 120 DEG C; Or 80 DEG C to 100 DEG C.Used by products obtained therefrom the conventional sieve plate screening of different size to just size.In some embodiments, chemistry (inorganic) fertilizer also can be used as carrier.
It will be understood by those skilled in the art that there is some change based on provided disclosure content.Therefore, provide following examples for the purpose of illustrating the invention, but should not be construed as the scope of the present invention or claim is limited.
Embodiment
Unless prepared granular preparation-clearly indicate in addition in this application, otherwise be the weight package of 90wt% or more based on the weight of granular preparation be the particle of 0.1mm to 10mm containing particle diameter.
To the assessment-plot of every block process is compared with the suitable untreated plot that contrasts that crop yield improves.Report the test is " DY% " (Δ output %), and it is defined as follows:
DY％＝100*[(Y
T-Y
U/Y
U]
Wherein Y
tthe output in the plot of=process, wherein Y
uthe output in=untreated plot.Such as, the DY of 10% refers to that the output in the plot of process is higher than the output in untreated plot by 10%.Negative Δ output refers to the output of the rice of process yielding poorly than untreated crop.
The stability of embodiment 1 – 1-MCP under carrier exists
For obtaining good field coverage rate, by increasing the volume of granular preparation with the dilution of at least one inert carrier.Use roll squeezer at HAIP (the high active ingredient particle of 0.1%1-MCP equivalent; The 1-MCP powder compounding with alpha-cyclodextrin) exist under carrier is tested.Analyze blend (before compacting) and test the chemical stability of material and the recycled materials passed through for the first time.
By all carriers 65 DEG C of (or 150 °F) dried overnight in advance, wherein residual moisture level is all near or below 0.5% except bentonite.Moisture on average about 2.61% after oven drying in bentonite.For the sake of clarity, only the data from recycled materials are shown in table 1.
According to chemical stability, think that lime stone and bentonite are best carrier.But auxiliary material may need to be added into these powder, to increase the granule integrity of these carriers, it is being difference at present and even is being very poor.
The other carrier of embodiment 2 –
Test three kinds of different types of clays in the described embodiment: sodium, calcium and activated bentonite clay.All clays all have start-up phase to high-caliber moisture (7% to 13%).In different hydration level, gypsum is tested: calcining (105 DEG C of dryings) and as dehydrate (deriving from Aldrich).By gypsum FGD 120 DEG C of dried overnight.Moisture level is reported in following table 2.All salt shows low-down moisture level (<1%).On the other hand, corn starch has the moisture (about 10%) of relative high levels.
Result is unexpected and surprising, and wherein dry clay does not increase stability, since it is known HAIP is to moisture-sensitive.Result shows, and the product compaction comprising the clay of some moisture is stablized than the product comprising dry clay.
But some carriers (such as, calcined gypsum and dehydrated form thereof) can bring out HAIP severely degrade, and no matter its moisture is how.In addition, result shows, and the salt (moisture level in the salt of these dryings is very low) of all dryings brings out HAIP obvious degradation.
For confirming the effect of moisture for stability, the result that studies for a long period of time is shown in Figure 2.Surprising discovery below results verification: the clay with some moisture can be useful to particle chemical stability.
Another tests display, and use inert binder not affect for increase stability, this is the moisture due to clay.From the sample containing corn starch binding agent and the stability data of sample not containing corn starch binding agent shown in Figure 3.
Embodiment 3 – release rate
About 600mg is comprised the sample that the sample of 0.1%1-MCP and 120mg comprise 0.5%1-MCP and be added into 250ml vial.Next, 5mlMilliQ water is added, by bottle capping.Bottle is slightly rotated, moistening sample, start release.When not further shake or rotary sample, per hourly to sample, continue 4 hours.After twenty four hours, sample is rotated 30 minutes on rotary drum, discharge any residual 1-MCP gas, then reanalyse.Result is shown in Figure 4.
As shown in Figure 4, compared to the sample (sample L, M and N) only containing 0.1%1-MCP, it is faster that the bentonite sample (sample O and P) comprising 0.5%1-MCP brings out release 1-MCP gas.The swelling generation water permeation of clay is made by during contact.Bentonite sodium clay can make swelling 8 to 10 times of its weight when moistening.Data show, and the release rate containing the sample of more clay and less 1-MCP is lower.In 0.5%1-MCP sample, HAIP contact water much rapid, when HAIP dissolves, more water permeation to the inside of particle, this produces the passage that gas is overflowed conversely.
Another tests display, and the dissolution rate being immersed in the water particle can be relevant to 1-MCP%.Result is shown in Figure 5.
Embodiment 4 – bentonite and limestone particle preparation
Use the rolling process of amendment, the particle (0.1%1-MCP and 0.5%1-MCP) of preparation two concentration.The advantage of compacting does not use liquid-containing binder, easily can be suitable for large-scale production.
In addition, chemical compatibility/stability and the granule integrity (particularly compression stress and wear resistence) of several carrier and dry binder and HAIP is tested.
Bentonite and lime stone show best total chemical stability and granule strength.The degraded that the display of these particles is only minimum when testing the chemical stability two weeks or longer at 54 DEG C.Add the preparation after molecular sieve to compacting, surprisingly, do not help chemical stability and undesirably granule strength be harmful to.Result is shown in Table 3.
When being immersed in the water completely, high concentration bentonite clay particle (0.5%1-MCP) discharged its active component (1-MCP) when not stirring in four (4) hours.The bentonite clay particle (0.1%1-MCP) of low concentration when not stirring within the twenty four hours time (one day) discharge much slow.Lime stone and bentonitic granular preparation are shown in Table 4 by moisture data after the pressure of %.
The other bentonite of embodiment 5 – and limestone particle preparation
Think that the moisture of bentonite and lime stone is important for the stability of granular preparation.Bentonite is less than 1% moisture by within 24 (24) hours, being dried to 104 DEG C of heating.But when described low-level moisture, under there is binding agent or there is not binding agent, bentonite compression becomes very ineffective.Add molecular sieve, for granule integrity, there is surprising negative effect.Test the physical stability of multiple bentonite and limestone particle preparation, result is shown in Table 5.
Sodium-bentonite and limestone particle are prepared with the micronized polyethylene binding agent of 5% or 15% respectively.All particle secondaries pass through, wherein 50% recycle fine powder.The result of compression and wear data is shown in Table 6 (mean values of two groups).
Embodiment 6 – headspace sample is analyzed
The AGF-B of 100 grams (0.5%1-MCP particle), batch B-3 are added into the bottle that 607ml is with thief hatch.By sample storage room temperature (RT), 38 DEG C or 50 ° 6 months, regularly sample.Isobutene is used as analytical standard.Data are shown in Table 7.
By sampling particle immediately in 250ml jug after roll squeezer compression, carry out headspace analysis.By about 1/3 of bottle with particles filled, with the airtight cover capping with thief hatch.Sample is once no longer open after capping.Headspace analysis can be expressed as the inflammability degree of simulation granular preparation after being stored in closed or confined space.
Even if in worst case (sample remains on 50 DEG C), head space number is also low, in most cases lower than 200ppm.At 38 DEG C and RT, head space, as a rule lower than 50ppm, shows the stability testing particulate samples.
Embodiment 7 – long-term stable experiment
HAIP is sieved, removes agglomerate with rider.Screen size is about 1mm or 18 orders.Then by blended for HAIP and the Volclay (AmericanColloidCompany, Illinois) of screening.Slightly mix in half-full vial, Glas-Col rotary drum rotates 10 minutes (speed: the full setting of 40%).The blend of preparation two concentration: 0.5%1-MCP and 1%1-MCP.The sample prepared in described embodiment is listed in table 8.
After compacting, bar is remained on room temperature or 54 DEG C, continuous stability test about six (6) individual months at the most.Granular preparation (1%1-MCP, moistening clay, not containing binding agent) the high-quality particle had on the whole of sample 7-3 and 7-4 is formed and chemical stability.After about six months, sample 7-3 and 7-4 prepared with the clay comprising 10% moisture, being no more than 3% total 1-MCP in room temperature loss, is 5% to 11% total 1-MCP 54 DEG C of losses.Other sample prepared with dry clay is more unstable, and wherein degrading in room temperature is 3% to 10% total 1-MCP, is 19% to 23% total 1-MCP at 54 DEG C.Great majority degraded occurred in aging first week.Significant difference is not seen between 0.5%1-MCP and 1.0%1-MCP.
Embodiment 8 – process rice plant
By the granular preparation of sample 7-3 and 7-4 for the treatment of the rice plant in wilderness.The 1-MCP of typical amount is treated to 10g active component (a.i.)/hectare (or 4ga.i./acre) to 100ga.i./hectare (or 40ga.i./acre).Best phenophase (phonologicalstages) of rice plant tillers to kernel grouting one of (such as at least: reduction division, wide-open flower, and kernel grouting) from maximum.Typically, before results, carry out the only single process of 1-MCP, but also can carry out multiple process of 1-MCP before results.The processes and displays output of 1-MCP on rice plant increases to 14% to 28%, and this depends on the amount of 1-MCP and the stage of process.The field test data of the single 50ga.i. of using/hectare 1-MCP is used to be shown in Table 9 to sample 7-3 (comprising the granular preparation of 1%1-MCP).
Claims (25)
1. granular preparation, it comprises
The molecular complex of (a) volatile compound and molecular encapsulation agent; With
B () moisture is the carrier component of 5% to 35%.
2. the granular preparation of claim 1, wherein said moisture is 7% to 15%.
3. the granular preparation of claim 1, wherein said carrier component comprises clay.
4. the granular preparation of claim 1, wherein said carrier component comprises bentonite, lime stone or its combination.
5. the granular preparation of claim 1, wherein said carrier component comprises sodium bentonite.
6. the granular preparation of claim 1, wherein said granular preparation does not comprise binder component.
7. the granular preparation of claim 1, wherein with do not have compared with control formulation that moisture is the carrier component of 5% to 35%, the chemical stability of described molecular complex is improved.
8. the granular preparation of claim 7, the improved chemical stability at least twice of wherein said molecular complex.
9. the granular preparation of claim 1, wherein said volatile compound comprises the compound cyclopropene of following formula:
Wherein R be replace or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl or naphthyl; Wherein said substituting group is halogen, alkoxyl or replace or unsubstituted phenoxy group independently.
10. the granular preparation of claim 9, wherein R is C
1-8alkyl.
The granular preparation of 11. claims 9, wherein R is methyl.
The granular preparation of 12. claims 1, wherein said volatile compound comprises the compound cyclopropene of following formula:
Wherein R
1for that replace or unsubstituted C
1-C
4alkyl, C
1-C
4thiazolinyl, C
1-C
4alkynyl, C
1-C
4cycloalkyl, cycloalkyl-alkyl, phenyl or naphthyl; R
2, R
3and R
4for hydrogen.
The granular preparation of 13. claims 1, wherein said compound cyclopropene comprises 1-methyl cyclopropene (1-MCP).
The granular preparation of 14. claims 13, wherein said granular preparation comprises the 1-MCP of 0.1% to 10%.
The granular preparation of 15. claims 14, wherein said granular preparation comprises the 1-MCP of 0.3% to 3%.
The granular preparation of 16. claims 1, wherein said molecular encapsulation agent is selected from alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin or its combination.
The granular preparation of 17. claims 1, wherein said molecular encapsulation agent comprises alpha-cyclodextrin.
18. methods making the molecular complex of volatile compound and molecular encapsulation agent stable, comprise use moisture be 5% to 35% carrier component prepare granular preparation.
19. for the preparation of the method for the granular preparation of claim 1, comprises and uses moisture to be the rolling process of the carrier component of 5% to 35%.
The method of 20. claims 19, does not use binding agent in wherein said rolling process.
The method of 21. claims 19, does not use molecular sieve in wherein said rolling process.
The method that 22. crop plants output increase and/or output is protected, described method comprises the field being applied to by the granular preparation of claim 1 and cultivating described crop plants, and wherein said crop plants was in reproduction period or maturing stage.
The method of 23. claims 22, wherein said crop plants is selected from rice plant, corn plant, wheat plant, bean plant, canola plant and vegetable lamb.
The method of 24. claims 22, wherein said granular preparation comprises 1-methyl cyclopropene (1-MCP).
The method of 25. claims 24, wherein the rate of application of 1-MCP is that 10g active component (a.i.)/hectare is to 100ga.i./hectare.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361845029P | 2013-07-11 | 2013-07-11 | |
| US61/845,029 | 2013-07-11 | ||
| PCT/US2014/046308 WO2015006667A1 (en) | 2013-07-11 | 2014-07-11 | Methods and compositions of granule formulations |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105377032A true CN105377032A (en) | 2016-03-02 |
| CN105377032B CN105377032B (en) | 2018-08-07 |
Family
ID=52280633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480038766.7A Expired - Fee Related CN105377032B (en) | 2013-07-11 | 2014-07-11 | The method and composition of granular preparation |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP3019007A4 (en) |
| JP (1) | JP6469672B2 (en) |
| KR (1) | KR20160030538A (en) |
| CN (1) | CN105377032B (en) |
| AR (1) | AR096871A1 (en) |
| AU (1) | AU2014287025B2 (en) |
| BR (1) | BR102014016880A2 (en) |
| CA (1) | CA2917341A1 (en) |
| CL (1) | CL2015003768A1 (en) |
| IL (1) | IL243331B (en) |
| MX (1) | MX2016000388A (en) |
| PE (1) | PE20160222A1 (en) |
| PH (1) | PH12016500053A1 (en) |
| RU (1) | RU2016104395A (en) |
| SG (1) | SG11201510772UA (en) |
| TW (1) | TW201534217A (en) |
| UY (1) | UY35657A (en) |
| WO (1) | WO2015006667A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3192290A (en) * | 1962-08-06 | 1965-06-29 | Minerals & Chem Philipp Corp | Method for producing rounded clay granules |
| US3931036A (en) * | 1974-05-13 | 1976-01-06 | Philadelphia Quartz Company | Compacted alkali metal silicate |
| CN1076721A (en) * | 1993-02-11 | 1993-09-29 | 亨克尔两合股份公司 | Be suitable as the particulate manufacture method of stain remover, washing composition and/or clean-out system |
| WO2008071714A1 (en) * | 2006-12-15 | 2008-06-19 | Rohm And Haas Company | Mixtures comprising 1-methylcyclopropene |
| US20120142534A1 (en) * | 2010-12-07 | 2012-06-07 | Mark Linden Dahmer | Granular compositions |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5718602A (en) * | 1980-05-28 | 1982-01-30 | Hokko Chem Ind Co Ltd | Herbicide |
| JPS5821602A (en) * | 1981-07-30 | 1983-02-08 | Hokko Chem Ind Co Ltd | Improved insecticidal and nematocidal preparation |
| US5650163A (en) * | 1986-11-24 | 1997-07-22 | American Cyanamid Company | Safened pesticidal resin compositions for controlling soil borne pests and process for the preparation thereof |
| JPH06219909A (en) * | 1993-01-26 | 1994-08-09 | Kumiai Chem Ind Co Ltd | Improved fungicide composition for agriculture |
| JPH08225404A (en) * | 1994-12-06 | 1996-09-03 | Takeda Chem Ind Ltd | Stabilized agrochemical preparation |
| US5647300A (en) * | 1995-10-31 | 1997-07-15 | First Brands Corporation | Compacted bentonite-based absorbents |
| US7247377B2 (en) * | 1999-09-17 | 2007-07-24 | Genaro Casas Jassan | Absorbent composition of matter for controlled release of essential oils |
| US6444619B1 (en) * | 2000-09-28 | 2002-09-03 | Rohm And Haas Company | Delivery system for cyclopropenes |
| US7034013B2 (en) * | 2001-03-20 | 2006-04-25 | Cydex, Inc. | Formulations containing propofol and a sulfoalkyl ether cyclodextrin |
| JP2006008658A (en) * | 2004-02-24 | 2006-01-12 | Sumitomo Chemical Takeda Agro Co Ltd | Insecticide composition |
| CA2504840C (en) * | 2004-05-05 | 2008-03-18 | Rohm And Haas Company | Humidity activated delivery systems for cyclopropenes |
| WO2009018069A2 (en) * | 2007-07-30 | 2009-02-05 | Cydex Pharmaceuticals, Inc | Mixtures of cyclodextrin derivatives |
| GB0812028D0 (en) * | 2008-07-01 | 2008-08-06 | Syngenta Participations Ag | Fungicidal compositions |
| KR101802004B1 (en) * | 2010-08-31 | 2017-11-27 | 다우 아그로사이언시즈 엘엘씨 | Pesticidal compositions |
| CN102119719B (en) * | 2010-12-10 | 2013-06-19 | 山东营养源食品科技有限公司 | Cyclopropene preservative, and preparation and packaging methods thereof |
| ES2729947T3 (en) * | 2011-07-12 | 2019-11-07 | Dow Agrosciences Llc | Pesticide compositions and related procedures |
-
2014
- 2014-07-04 TW TW103123180A patent/TW201534217A/en unknown
- 2014-07-09 BR BRBR102014016880-0A patent/BR102014016880A2/en not_active Application Discontinuation
- 2014-07-10 UY UY35657A patent/UY35657A/en not_active Application Discontinuation
- 2014-07-10 AR ARP140102555A patent/AR096871A1/en unknown
- 2014-07-11 WO PCT/US2014/046308 patent/WO2015006667A1/en active Application Filing
- 2014-07-11 KR KR1020167003038A patent/KR20160030538A/en not_active Application Discontinuation
- 2014-07-11 JP JP2016525799A patent/JP6469672B2/en not_active Expired - Fee Related
- 2014-07-11 RU RU2016104395A patent/RU2016104395A/en not_active Application Discontinuation
- 2014-07-11 EP EP14823639.1A patent/EP3019007A4/en not_active Withdrawn
- 2014-07-11 SG SG11201510772UA patent/SG11201510772UA/en unknown
- 2014-07-11 CA CA2917341A patent/CA2917341A1/en not_active Abandoned
- 2014-07-11 MX MX2016000388A patent/MX2016000388A/en unknown
- 2014-07-11 AU AU2014287025A patent/AU2014287025B2/en not_active Ceased
- 2014-07-11 PE PE2016000033A patent/PE20160222A1/en unknown
- 2014-07-11 CN CN201480038766.7A patent/CN105377032B/en not_active Expired - Fee Related
-
2015
- 2015-12-24 IL IL243331A patent/IL243331B/en not_active IP Right Cessation
- 2015-12-30 CL CL2015003768A patent/CL2015003768A1/en unknown
-
2016
- 2016-01-07 PH PH12016500053A patent/PH12016500053A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3192290A (en) * | 1962-08-06 | 1965-06-29 | Minerals & Chem Philipp Corp | Method for producing rounded clay granules |
| US3931036A (en) * | 1974-05-13 | 1976-01-06 | Philadelphia Quartz Company | Compacted alkali metal silicate |
| CN1076721A (en) * | 1993-02-11 | 1993-09-29 | 亨克尔两合股份公司 | Be suitable as the particulate manufacture method of stain remover, washing composition and/or clean-out system |
| WO2008071714A1 (en) * | 2006-12-15 | 2008-06-19 | Rohm And Haas Company | Mixtures comprising 1-methylcyclopropene |
| US20120142534A1 (en) * | 2010-12-07 | 2012-06-07 | Mark Linden Dahmer | Granular compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3019007A1 (en) | 2016-05-18 |
| WO2015006667A1 (en) | 2015-01-15 |
| JP2016528208A (en) | 2016-09-15 |
| SG11201510772UA (en) | 2016-01-28 |
| EP3019007A4 (en) | 2016-11-16 |
| TW201534217A (en) | 2015-09-16 |
| RU2016104395A (en) | 2017-08-16 |
| JP6469672B2 (en) | 2019-02-13 |
| KR20160030538A (en) | 2016-03-18 |
| AU2014287025A1 (en) | 2016-01-28 |
| AR096871A1 (en) | 2016-02-03 |
| AU2014287025B2 (en) | 2017-03-23 |
| IL243331B (en) | 2019-07-31 |
| CL2015003768A1 (en) | 2016-08-12 |
| PE20160222A1 (en) | 2016-04-20 |
| PH12016500053A1 (en) | 2016-03-28 |
| BR102014016880A2 (en) | 2015-03-17 |
| UY35657A (en) | 2015-02-27 |
| MX2016000388A (en) | 2016-04-29 |
| IL243331A0 (en) | 2016-02-29 |
| CN105377032B (en) | 2018-08-07 |
| CA2917341A1 (en) | 2015-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pereira et al. | Controlled urea release employing nanocomposites increases the efficiency of nitrogen use by forage | |
| Benício et al. | Layered double hydroxides: new technology in phosphate fertilizers based on nanostructured materials | |
| Sempeho et al. | Meticulous overview on the controlled release fertilizers | |
| Wang et al. | κ-Carrageenan–sodium alginate beads and superabsorbent coated nitrogen fertilizer with slow-release, water-retention, and anticompaction properties | |
| US10287217B2 (en) | Method for manufacturing sustained-release matrix-type granular complex fertilizer and matrix-type granular complex fertilizer obtained therefrom | |
| Nennemann et al. | Clay-based formulations of metolachlor with reduced leaching | |
| CA2839535C (en) | Coated seeds | |
| US20170156315A1 (en) | Methods and compositions of granule formulations | |
| BR112018068071B1 (en) | SOIL QUALITY IMPROVEMENT METHOD, SOIL QUALITY IMPROVEMENT AGENT, AND SOIL QUALITY IMPROVEMENT AGENT COMPOSITION | |
| CN103553763B (en) | Agricultural composition containing chitosan oligosaccharide and fipronil | |
| Hosseinpur et al. | Potassium release kinetics and its correlation with pinto bean (Phaseolus vulgaris) plant indices. | |
| Park et al. | Intercalation of magnesium–urea complex into swelling clay | |
| CA2957925A1 (en) | Ultra lightweight clay and polymer high performance clumping cat litter | |
| CN113683455A (en) | Functional organic and inorganic fertilizer and preparation method thereof | |
| RU2566684C1 (en) | Multicomponent organic-mineral fertiliser | |
| CN105377032A (en) | Methods and compositions of granule formulations | |
| EP4077244A1 (en) | Use of granular pyrolytic carbon for soil conditioning | |
| Haron et al. | Palm-based bio-fertilizer from decanter cake and boiler ash of palm oil mill | |
| CN103768632A (en) | Natural mineral odor-removing agent | |
| BR112020005956B1 (en) | PLANT GROWTH PROMOTER, METHOD FOR PRODUCING A PLANT GROWTH PROMOTER, AND METHOD FOR CULTIVATING A PLANT | |
| RU2713692C1 (en) | Method of preparing organosilicon fertilizer | |
| CN107827569A (en) | A kind of organic substrate fertilizer for flower planting | |
| RU2243639C1 (en) | Method for presowing treatment of seeds | |
| JP2004283060A (en) | Culture medium for mat plant, granular culture medium for mat plant, and method for constructing greening using the medium | |
| JPH0280388A (en) | Compound fertilizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180807 Termination date: 20200711 |