CN104837341A

CN104837341A - Oil formulations with thickeners

Info

Publication number: CN104837341A
Application number: CN201380063258.XA
Authority: CN
Inventors: R·M·雅各布森
Original assignee: AgroFresh Inc
Current assignee: AgroFresh Inc
Priority date: 2012-10-05
Filing date: 2013-09-11
Publication date: 2015-08-12
Anticipated expiration: 2033-09-11
Also published as: PH12015500717A1; AU2013325149B2; BR112015007339A2; KR20150065792A; CN104837341B; CA2886520A1; NZ706334A; IN2015DN02680A; JP2015530474A; RU2015116683A; ZA201502709B; MX2015004104A; CL2015000847A1; SG11201502387QA; EP2903433A4; EP2903433A2; WO2014055208A3; WO2014055208A2; IL238065B; CR20150220A

Abstract

This invention is based on unexpected effect of at least one thickener to maintain suspension or dispersion of solid particles in an oil medium. Such effect of thickener enables significant higher weight ratio of solid particles in such suspension composition as compared to previously known compositions. As a consequence, the suspension compositions provided herein enable more active ingredient in the solid particle to be present in a fixed volume or weight of such composition as compared to previously known compositions. One advantage of the suspension composition provided herein can be for aerial spraying of active ingredient such as herbicides, insecticides, or other growth regulating compounds.

Description

Oil formulation containing thickener

The cross reference of related application

The application requires the priority of the U.S. Provisional Application 61/710,019 that on October 5th, 2012 submits under 35U.S.C. § 119 (e), and its disclosure is especially by reference to being incorporated to the application.

Background technology

For the purposes of cyclopropylene, the form of cyclopropylene is generally the compound with molecular encapsulation agent.Such compound is useful, such as, for by making plant or plant part with complex contacts so that make plant or formed between plant part and cyclopropylene to contact to process plant or plant part.Usually be effective in the process desirably hindering the one or more ethene in plant or plant part to regulate to this process of plant or plant part.Such as, sometimes unwanted maturation can desirably be postponed to this process of plant part.For another example, before harvesting, sometimes can improve crop from output to this process of crop plants.

US 6,313,068 discloses and the dried powder of the compound of cyclodextrin and methyl cyclopropene is ground and milled.

Usually usefully, by the grain dissolution of this compound or float on a liquid.But if water is liquid, then sometimes find that the contact between water and composite particles causes cyclopropylene from the release ratio expection compound early, some or all of therefore cyclopropylene are lost in surrounding environment or are destroyed by chemical reaction or combine for it.Therefore, usually expect such particle is suspended in oil.But, in the past, have been found that and make the trial be suspended in oil of such particle that such particle can not be made effectively to be suspended in oil, normally because suspension can not suitably spray, or because suspension has too high viscosity at rational granule density, or because suspension is unstable or suspension sedimentation or become creaminess, or because suspension has some combinations of these problems.The object of this invention is to provide the one or more suspension of the particle comprising cyclopropylene compound in oil in can addressing these problems.

Summary of the invention

The present invention is based on following unexpected effect, at least one thickener makes solid particle keep suspending or being dispersed in oily medium.The such effect of thickener can make the solid particle that there is remarkable higher weight ratio in such suspension composition, compared with composition known before.Therefore, the suspension composition that the application provides can make active component more in solid particle be present in such composition of fixed volume or weight, compared with composition known before.An advantage of the suspension composition that the application provides can be aerial spraying active component such as weed killer herbicide, insecticide or other growth regulating compound.Other advantage of the suspension composition that the application provides comprises the release of the cyclopropylene that slows down, and reduces the payload weight being used for aircraft and the helicopter used in the air.

This application provides cyclopropylene/cyclodextrin complexes containing the suspension in the hydrophobic fluid of auxiliary material, it can form the system for controlling to send cyclopropylene.

On the one hand, this application provides the composition of bag oil containing medium and at least one thickener, wherein composition is the suspension of solid particle in oily medium, and solid particle comprises cyclopropylene and molecular encapsulation agent.

In one embodiment, suspension does not precipitate and reaches at least two weeks, at least surrounding, at least eight weeks, at least two ten weeks or at least four ten weeks.In another embodiment, oily medium is selected from white mineral oil, hydrotreated middle petroleum distillate, hydrotreated light petroleum fraction, and combination.In further embodiment, white mineral oil comprises Blandol and/or Klearol.In the further embodiment of another kind, hydrotreated middle petroleum distillate comprises Conosol 260, Unipar SH 260CC, and/or Isopar V.In the further embodiment of another kind, hydrotreated light petroleum fraction comprises Unipar SH 210AS and/or Isopar M.

In one embodiment, 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, alkoxyl or substituted or unsubstituted phenoxy group independently.

In further embodiment, R is C _1-8alkyl.In another embodiment, R is methyl.

In another embodiment, compound cyclopropene has following formula:

Wherein R ¹substituted 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 ⁴hydrogen.

In one embodiment, cyclopropylene comprises 1-methyl cyclopropene (1-MCP).In another embodiment, molecular encapsulation agent is selected from the cyclodextrin of replacement, unsubstituted cyclodextrin, and combination.In further embodiment, molecular encapsulation agent comprises alpha-cyclodextrin.

In one embodiment, solid particle accounts at least 5 % by weight, at least 10 % by weight, at least 20 % by weight, at least 30 % by weight, at least 40 % by weight, at least 50 % by weight or at least 60 % by weight of composition.In another embodiment, solid particle accounts for 10-20 % by weight, the 10-30 % by weight of composition, 10-40 % by weight, 10-50 % by weight, 10-60 % by weight, 20-40 % by weight, 30-60 % by weight or 40-60 % by weight.In another embodiment, composition comprises the 1-methyl cyclopropene (1-MCP) of at least 5 % by weight, at least 10 % by weight, at least 20 % by weight, at least 30 % by weight, at least 40 % by weight, at least 50 % by weight or at least 60 % by weight and the compound of alpha-cyclodextrin.In another embodiment, composition comprises the 1-methyl cyclopropene (1-MCP) of 10-20 % by weight, 10-30 % by weight, 10-40 % by weight, 10-50 % by weight, 10-60 % by weight, 20-40 % by weight, 30-60 % by weight or 40-60 % by weight and the compound of alpha-cyclodextrin.

In one embodiment, composition comprises at least one thickener of at least 1 % by weight, at least 3 % by weight, at least 5 % by weight, at least 10 % by weight, at least 15 % by weight, at least 20 % by weight, at least 30 % by weight, at least 40 % by weight or at least 50 % by weight.In another embodiment, composition comprises at least one thickener of 1-20 % by weight, 1-30 % by weight, 1-40 % by weight, 1-50 % by weight, 5-20 % by weight, 5-40 % by weight, 10-50 % by weight or 20-50 % by weight.In another embodiment, at least one thickener comprises based on cellulosic thickener.In another embodiment, at least one thickener comprises polymer viscosifier.In further embodiment, polymer viscosifier is formed by least one in acrylate, alkyl acrylate and acid anhydride.In the further embodiment of another kind, polymer viscosifier comprises at least one and is selected from following component: polypropylene, polyisoprene, polybutadiene, poly-(styrene-butadiene), poly-(styrene-ethylene/propylene), poly-(Ethylene-Propylene-Diene), polyurethane, polymethacrylates, polyisobutene, poly-(isobutene-succinic acid), poly-(isobutene-succinic acid-polyacrylamide), polyureas, polyethylene, and combination.

In another embodiment, polymer viscosifier comprises the first component and second component, and wherein the weight average molecular weight of the first component is higher than the weight average molecular weight of second component.In further embodiment, the weight ratio of the first component and second component is at least 1:5, at least 1:10, at least 1:20, at least 1:30, at least 1:40 or at least 1:50.In the further embodiment of another kind, the weight ratio of the first component and second component is 1:5 to 1:20; 1:10 to 1:40, or 1:5 to 1:50.In another embodiment, polymer viscosifier does not comprise ethylene, propylene norbornadiene copolymer.In further embodiment, such ethylene, propylene norbornadiene copolymer does not comprise Nordel IP3745P.In another embodiment, polymer viscosifier does not comprise styrene ethylene/propylene copolymer.In further embodiment, such styrene ethylene/propylene copolymer does not comprise Septon 1020 or Septon 1001.

On the other hand, this application provides the method for supending composition, comprise (a) and put in medium grinder by material, described material comprises the compound of cyclopropylene and molecular encapsulation agent, oily medium and at least one thickener; (b) described material is ground to form the composition comprising solid particle.

In one embodiment, suspension composition does not precipitate and reaches at least two weeks, at least surrounding, at least eight weeks, at least two ten weeks or at least four ten weeks.In another embodiment, oily medium is selected from white mineral oil, hydrotreated middle petroleum distillate, hydrotreated light petroleum fraction, and combination.In further embodiment, white mineral oil comprises Blandol and/or Klearol.In the further embodiment of another kind, hydrotreated middle petroleum distillate comprises Conosol 260, Unipar SH 260CC, and/or Isopar V.In the further embodiment of another kind, hydrotreated light petroleum fraction comprises Unipar SH 210AS and/or Isopar M.

In one embodiment, compound cyclopropene has following formula:

In further embodiment, R is C _1-8alkyl.In another embodiment, R is methyl.

In another embodiment, compound cyclopropene has following formula:

In one embodiment, composition comprises the 1-methyl cyclopropene (1-MCP) of at least 5 % by weight, at least 10 % by weight, at least 20 % by weight, at least 30 % by weight, at least 40 % by weight, at least 50 % by weight or at least 60 % by weight and the compound of alpha-cyclodextrin.In another embodiment, composition comprises the 1-methyl cyclopropene (1-MCP) of 10-20 % by weight, 10-30 % by weight, 10-40 % by weight, 10-50 % by weight, 10-60 % by weight, 20-40 % by weight, 30-60 % by weight or 40-60 % by weight and the compound of alpha-cyclodextrin.

Embodiment

When the application's applying unit " ppm " describe compound exist using finite concentration as gas in an atmosphere time, this concentration is given as the air for every 1,000,000 parts by volume, the parts by volume of this compound.Similarly, " ppb " represents the air for every 1,000,000,000 parts by volume, the parts by volume of this compound.

The present invention relates to and use one or more compound cyclopropenes.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 0-12.The each divalent group naturally of L.Suitable L group comprises, such as, containing one or more group being selected from the atom of H, B, C, N, O, P, S, Si or its combination.The atom of L group can be interconnected by singly-bound, double bond, triple bond or its combination.L group can be linear, branching, ring-type or its combination separately.At any one R group (i.e. R ¹, R ², R ³and R ⁴in any one) in, hetero atom (that is, neither hydrogen neither the atom of carbon) add up to 0-6.

Independently, in any one R group, non-hydrogen atom add up to 50 or less.

The each univalent perssad naturally of Z.Z is selected from hydrogen, halogen, cyano group, nitro, nitroso, azido, chlorate anions, bromate, iodate, isocyano group (isocyanato), isonitrile base (isocyanido), isothiocyano, five fluorine sulfenyls and chemical group G independently of one another, and wherein G is 3-14 unit ring system.

R ¹, R ², R ³and R ⁴group is independently selected from suitable group.R ¹, R ², R ³and R ⁴group can be mutually the same, or they of any number can be different from other.Be suitable for being used as R ¹, R ², R ³and R ⁴in one or more groups be especially; such as, aliphatic group, aliphatic oxygen base group, alkylphosphines acid group (alkyl phosphonato) group, cycloaliphatic groups, naphthene sulfamide base, cycloalkyl amino, heterocyclic group, aryl, heteroaryl, halogen, silicyl, other group, and composition thereof with combination etc.Be suitable for being used as R ¹, R ², R ³and R ⁴in one or more groups can be substituted or unsubstituted.Independently, be suitable for being used as R ¹, R ², R ³and R ⁴in one or more groups can be directly connected in cyclopropylene ring or such as can be connected to cyclopropylene ring containing heteroatomic group by group therebetween.

Suitable R ¹, R ², R ³and R ⁴group especially, such as, aliphatic group.Some suitable aliphatic groups comprise, such as, and alkyl, thiazolinyl and alkynyl.Suitable aliphatic group can be linear, branching, ring-type or its combination.Independently, suitable aliphatic group can be substituted or unsubstituted.

As used in this application, if one or more hydrogen atoms of useful chemical group are substituted with a substituent, then think that useful chemical group is " replacement ".Think, the group of such replacement can be prepared by any method, includes but not limited to prepare the useful chemical group not replacing form, then replaces.Suitable substituting group comprises, such as, and alkyl, thiazolinyl, acetylamino, alkoxyl; alkyloxy-alkoxy, alkoxy carbonyl, Alkoximino, carboxyl, halogen, halogenated alkoxy; hydroxyl, alkyl sulphonyl, alkyl sulfenyl, trialkylsilkl, dialkyl amido, and combination.If existed, any suitable substituting group in addition can individualism or substituent combine suitable with another kind exist, and it is

-(L) _m-Z

Wherein m is 0 to 8, and wherein L and Z in the restriction above of the application.If more than one substituting group is present on single useful chemical group, then each substituting group can substitute different hydrogen atoms, or a substituting group can be connected to another substituting group, and it is thus connected in useful chemical group, or its combination.

Suitable R ¹, R ², R ³and R ⁴group especially, such as, replaces and unsubstituted aliphatic series-oxygen base group, such as, and alkene oxygen base, alkoxyl, alkynyloxy group, and alkoxy-carbonyl oxy.

Equally, suitable R ¹, R ², R ³and R ⁴group especially; such as; replace and unsubstituted alkylphosphines acid group (alkylphosphonato); replace and unsubstituted alkyl phosphoric acid root (alkylphosphato); replace and unsubstituted alkyl amino; replace and unsubstituted alkyl sulphonyl, replace and unsubstituted alkyl-carbonyl, and replace and unsubstituted alkyl amino sulfonyl; comprise; such as, alkylphosphines acid group, Acidic phosphates root; dialkyl phosphate radical; dialkyl amido, alkyl-carbonyl, and dialkyl amino sulfonyl.

Equally, suitable R ¹, R ², R ³and R ⁴group especially, such as, replaces and unsubstituted naphthene sulfamide base and cycloalkyl amino, such as, and bicyclic alkyl amino sulfonyl and bicyclic alkyl amino.

Equally, suitable R ¹, R ², R ³and R ⁴group especially, such as, replaces and unsubstituted heterocyclyl groups (that is, having at least one heteroatomic aromatics or non-aromatic cyclic groups in ring).

Equally, suitable R ¹, R ², R ³and R ⁴group especially, such as, is connected to the replacement of compound cyclopropene and unsubstituted heterocyclyl groups by oxygen base, amino, carbonyl or sulfonyl therebetween; Such R ¹, R ², R ³and R ⁴the example of group is heterocyclyloxy base, Heterocyclylcarbonyl, two heterocyclylamino group, and two heterocyclylamino group sulfonyls.

Equally, suitable R ¹, R ², R ³and R ⁴group especially, such as, replaces and unsubstituted aryl.Suitable substituting group be the application above-described those.In some embodiments, use the aryl of one or more replacement, wherein at least one substituting group is one or more in following group: thiazolinyl, alkyl; alkynyl, acetylamino, alkyloxy-alkoxy, alkoxyl; alkoxy carbonyl, carbonyl, alkyl-carbonyl oxygen base, carboxyl; arylamino, halogenated alkoxy, halogen, hydroxyl; trialkylsilkl, dialkyl amido, alkyl sulphonyl, Sulfonylalkyl; alkyl sulfenyl, alkylthio, n-aryl sulfonyl, and haloalkylthio.

Equally, suitable R ¹, R ², R ³and R ⁴group especially, such as, is connected to the replacement of compound cyclopropene and unsubstituted heterocyclyl groups by oxygen base, amino, carbonyl, sulfonyl, alkylthio or amino-sulfonyl therebetween; Such R ¹, R ², R ³and R ⁴the example of group is and heteroaryl amino, Heteroarylthio alkyl, and two heteroarylaminosulfonyl.

Equally, suitable R ¹, R ², R ³and R ⁴group especially, such as, hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, nitroso, azido, chlorate anions, bromate, iodate, isocyano group (isocyanato), isonitrile base (isocyanido), isothiocyano, five fluorine sulfenyls; Acetoxyl group, formyl ethyoxyl (carboethoxy), cyanic acid base, nitrato, nitrito-, perchloryl, allene base; Butyl sulfydryl, diethyl phosphonic acids foundation, dimethylphenylsilyl, isoquinolyl, sulfydryl, naphthyl, phenoxy group, phenyl, piperidyl, pyridine radicals, quinolyl, triethylsilyl, trimethyl silyl; And the analog replaced.

As used in this application, chemical group G is 3 to 14 yuan of ring systems.The suitable ring system as chemical group G can be substituted or unsubstituted; They can be (the comprising unsaturated aliphatic, fractional saturation aliphatic series or radical of saturated aliphatic) of aromatics (comprising such as phenyl and naphthyl) or aliphatic series; They can be carbocyclic ring or heterocycle.In heterocycle G group, some suitable hetero atoms are, such as, and nitrogen, sulphur, oxygen and combination thereof.The suitable ring system as chemical group G can be monocycle, two rings, three rings, many rings, volution or condense; Suitable be two rings, in three rings or the chemical group G ring system that condenses, each ring in single chemical group G can be all identical type or can be two or more types (such as aromatic ring can condense with aliphatic ring).

In some embodiments, G is the ring system comprising saturated or unsaturated 3 rings, such as, replaces or undersaturated cyclopropane, cyclopropylene, epoxides or ethylene imine ring.

In some embodiments, G is the ring system comprising 4 yuan of heterocycles; In some such embodiments, heterocycle accurately comprises a hetero atom.Independently, in some embodiments, G is the ring system comprising 5 yuan or more first heterocycles; In some such embodiments, heterocycle comprises 1 to 4 hetero atom.Independently, in some embodiments, the ring in G is unsubstituted; In other embodiments, ring system comprises 1 to 5 substituting group; G comprises in more substituent embodiments wherein, and substituting group is selected from the application's substituting group mentioned above independently of one another.Equally desirably wherein G is the embodiment of carbocyclic ring system.

In some embodiments, G is substituted or unsubstituted phenyl, pyridine radicals, cyclohexyl, cyclopenta, suberyl, pyrrole radicals, furyl, thienyl, triazolyl, pyrazolyl, DOX base or morpholinyl independently of one another.These embodiments especially comprise those embodiments following, and such as, wherein G is the phenyl, cyclopenta, suberyl or the cyclohexyl that do not replace or replace.In some such embodiments, G be cyclopenta, suberyl, cyclohexyl, phenyl or replace phenyl.Wherein G is the especially following embodiment of embodiment of the phenyl replaced, and such as, wherein can there are 1,2 or 3 substituting groups.Independently, wherein G is the embodiment also especially following embodiment of the phenyl replaced, and such as, wherein substituting group is independently selected from methyl, methoxyl group and halogen.

Also spendable is following embodiment, wherein R ³and R ⁴be combined into separate base, it is connected to No. 3 carbon atoms of cyclopropylene ring by double bond.Some of such compound are described in U.S. Patent Publication 2005/0288189.

In some embodiments, one or more cyclopropylene are used, wherein R ¹, R ², R ³and R ⁴in one or more be hydrogen.In some embodiments, R ¹or R ², or R ¹and R ²both are hydrogen.Independently, in some embodiments, R ³or R ⁴, or R ³and R ⁴both are hydrogen.In some embodiments, R ², R ³, and R ⁴hydrogen.

In some embodiments, R ¹, R ², R ³and R ⁴in one or more are the structures without double bond.Independently, in some embodiments, R ¹, R ², R ³and R ⁴in one or more are the structures without triple bond.Independently, in some embodiments, R ¹, R ², R ³and R ⁴in one or more be not containing the structure of halogen atom substituent.Independently, in some embodiments, R ¹, R ², R ³and R ⁴in one or more are the structures not having ion substituent.

In some embodiments, R ¹, R ², R ³and R ⁴in one or more be hydrogen or (C ₁-C ₁₀) alkyl.In some embodiments, R ¹, R ², R ³and R ⁴each hydrogen or (C naturally ₁-C ₈) alkyl.In some embodiments, R ¹, R ², R ³and R ⁴each hydrogen or (C naturally ₁-C ₄) alkyl.In some embodiments, R ¹, R ², R ³and R ⁴each hydrogen or methyl naturally.In some embodiments, R ¹(C ₁-C ₄) alkyl, and R ², R ³and R ⁴each hydrogen naturally.In some embodiments, R ¹methyl, and R ², R ³and R ⁴each hydrogen naturally, compound cyclopropene is called 1-methyl cyclopropene or " 1-MCP " in the application.

In some embodiments, being used in an atmospheric boiling point is 50 DEG C or lower; Or 25 DEG C or lower; Or 15 DEG C or lower cyclopropylene.Independently, in some embodiments, be used in an atmospheric boiling point and be-100 DEG C or higher;-50 DEG C or higher; Or-25 DEG C or higher; Or 0 DEG C or higher cyclopropylene.

Cyclopropylene used in the present invention can be prepared by any method.Some the suitable methods preparing cyclopropylene are disclosed in United States Patent (USP) 5,518,988 and 6,017, the method for 849.

Composition of the present invention can comprise at least one molecular encapsulation agent.In some embodiments, at least one molecular encapsulation agent encapsulates a part for one or more cyclopropylene or one or more cyclopropylene.The compound comprising the part being encapsulated in cyclopropene molecular in molecular encapsulation agent molecule or cyclopropene molecular is called " cyclopropylene compound " in the application.

In some embodiments, there is at least one cyclopropylene compound, i.e. inclusion complex (inclusion complex).In this inclusion complex, molecular encapsulation agent forms hole, and a part for cyclopropylene or cyclopropylene is positioned at this hole.Such inclusion complex some in, do not exist covalently bound between cyclopropylene and molecular encapsulation agent.Independently, such inclusion complex some in, between cyclopropylene and molecular encapsulation agent, there is not ion connect, whether there is any electrostatic attraction regardless of between the one or more polar portion in cyclopropylene and the one or more polar portions in molecular encapsulation agent.

Independently, such inclusion complex some in, the inside, hole of molecular encapsulation agent is nonpolar or hydrophobic substantially, or both, and cyclopropylene (or part being positioned at hole of cyclopropylene) is also nonpolar or hydrophobic substantially, or both.Although the present invention is not limited to any special theory or mechanism, think, in this nonpolar cyclopropylene compound, Van der Waals force or hydrophobic interaction or cyclopropene molecular or its part both it, can be made to remain in the hole of molecular encapsulation agent.

Cyclopropene molecular encapsulation agent compound can be prepared by any method.In a kind of preparation method, such as, such compound is prepared as follows: the solution or the slurry liquid contacts that make cyclopropylene and molecular encapsulation agent, then use and be such as disclosed in United States Patent (USP) 6,017, disclosed in 849, compound is separated by method.Such as, what cyclopropylene was encapsulated in molecular encapsulation agent wherein prepares in a kind of method of compound, and by cyclopropylene gas sparging by the solution of molecular encapsulation agent in water, first compound is from this precipitation, then passes through isolated by filtration.In some embodiments, compound is prepared by above method, and is dried after releasing and (such as powder) storage in solid form, to add to after a while in useful composition.

The useful feature of the amount of molecular encapsulation agent be molecular encapsulation agent molal quantity and cyclopropylene molal quantity ratio.In some embodiments, molecular encapsulation agent molal quantity and cyclopropylene molal quantity ratio can be 0.1 or larger; 0.2 or larger; 0.5 or larger; Or 0.9 or larger.Independently, in some such embodiments, molecular encapsulation agent molal quantity and cyclopropylene molal quantity ratio can be 2 or less; Or 1.5 or less.

Suitable molecular encapsulation agent comprises, such as, and organic and inorganic molecule encapsulation agent.Suitable organic molecule encapsulation agent comprises, such as, and the cyclodextrin of replacement, unsubstituted cyclodextrin and crown ether.Suitable inorganic molecule encapsulation agent comprises, such as, and zeolite.The mixture having suitable molecular encapsulation agent suitable equally.In some embodiments, molecular encapsulation agent is alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin or its mixture.In certain embodiments of the present invention, alpha-cyclodextrin is used.Structure according to one or more cyclopropylene to be used changes by preferred encapsulation agent.According to the present invention, the mixture of any cyclodextrin or cyclodextrin, cyclodextrin, the cyclodextrin of modification or its mixture also can be used.Some cyclodextrin purchased from, such as, Wacker Biochem Inc., Adrian, MI or Cerestar USA, Hammond, IN, and other supplier.

In the practice of the invention, one or more oil is used.As used in this application, term " oil " refers to and is liquid at 25 DEG C and 1 atmospheric pressure and is 30 DEG C or higher compound at 1 atmospheric boiling point.As used in this application, " oil " does not comprise water, does not comprise surfactant (as described in the present application), does not also comprise dispersant (as described in the present application).

In some embodiments, one or more boiling points can be used to be 50 DEG C or higher or 75 DEG C or higher or 100 DEG C or higher oil.In some embodiments, often kind that uses oily boiling point is 50 DEG C or higher.In some embodiments, often kind that uses oily boiling point is 75 DEG C or higher.In some embodiments, often kind that uses oily boiling point is 100 DEG C or higher.Independently, use oil some embodiments in, can use mean molecule quantity be 100 or higher or 200 or higher or 500 or higher one or more oil.In some embodiments, often kind that uses oily mean molecule quantity is 100 or higher.In some embodiments, often kind that uses oily mean molecule quantity is 200 or higher.In some embodiments, often kind that uses oily mean molecule quantity is 500 or higher.

Oil can be hydrocarbon ils (that is, its molecule only comprises the oil of carbon atom and hydrogen atom) or non-hydrocarbon ils (that is, its molecule comprises at least one neither carbon neither the oil of atom of hydrogen).

Some suitable hydrocarbon ils are, such as, have the alkane compound of the straight chain of 6 or more carbon atoms, branching or ring-type.Some other suitable hydrocarbon ils such as have one or more carbon-to-carbon double bond, one or more carbon-to-carbon triple bond, one or more aromatic ring, and it may combination with one another and/or combine with one or more alkane group.Some suitable hydrocarbon ils can obtain from petroleum distillate, and the mixture of inclusion compound and impurity in some cases.The mixture that the hydrocarbon ils obtained from petroleum distillate can comprise relatively wide component maybe can comprise relatively pure component.In some embodiments, the hydrocarbon oil used is containing 6 or more carbon atoms.In some embodiments, the hydrocarbon oil used is containing 18 or less carbon atom.In some embodiments, the often kind of hydrocarbon ils used all comprises 18 or less carbon atom.In some embodiments, the often kind of hydrocarbon ils used all comprises 6 or more carbon atoms.Some suitable hydrocarbon ils comprise, and such as, the paraffin oil of hexane, decane, dodecane, hexadecane, diesel oil, hydrotreated light petroleum fraction, hydrotreated middle petroleum distillate, refining is (such as from the Ultrafine of Sun Company ^tMspray oil) and composition thereof.In some embodiments, the often kind of oil used is all hydrocarbon ils.

In the embodiment using non-hydrocarbon ils, some suitable non-hydrocarbon ils are, such as, and fatty non-hydrocarbon ils." fat " refers to any compound comprising one or more residues of fatty acid in the application.The long-chain carboxylic acid of fatty acid to be chain length be at least 4 carbon atoms.The chain length of typical fatty acid is 4 to 18 carbon atoms, but some have longer chain.Linearly, the aliphatic group of branching or ring-type can be connected to long-chain.Fatty acid residue can be saturated or undersaturated, and they can comprise functional group, and described functional group comprises such as alkyl, epoxide group, halogen, sulfonic acid group or hydroxyl, and they can naturally occurring or add.The non-hydrocarbon ils of some suitable fat is, such as, and fatty acid; Fatty acid ester; Fatty acid amide; Its dimer, trimer, oligomer or polymer; And composition thereof.

The non-hydrocarbon ils of some suitable fat is, such as, and fatty acid ester.Such ester comprises, such as, and fatty glyceride.Glyceride is the ester of fatty acid and glycerine, and they can be monoglyceride, diglyceride or triglycerides.Multiple triglycerides has been found in nature.The naturally occurring triglycerides of major part comprises the fatty acid residue with multiple different length and/or composition.Some suitable triglycerides are found in animal origin, such as dairy products, animal tallow or fish.The further example of suitable triglycerides is the oil being found in plant, and such as cocounut oil, palm oil, cottonseed oil, olive oil, pine tar, peanut oil, safflower oil, sunflower oil, corn oil, soybean oil, linseed oil, tung oil, castor oil, Tower rape oil, citrus seeds oil, cupu oil, oat oil, palm oil, palm-kernel oil, rice bran oil, positive calyx are apart from caul-fat (cupheaoil) or rapeseed oil.

No matter be found in where, suitable triglycerides especially, such as, has those of the fatty acid residue of 14 or more carbon atoms containing at least one.The weight package that some suitable triglycerides have based on residue has the fatty acid residue of 14 or more carbon atoms containing 50 % by weight or more or has the fatty acid residue of 16 or more carbon atoms or have the fatty acid residue of fatty acid residue of 18 or more carbon atoms.An example of suitable triglycerides is soybean oil.

The non-hydrocarbon ils of suitable fat can be modifier or its combination or the mixture of artificial oil or natural oil or natural oil.The modification of suitable natural oil is especially, such as, and alkylation, hydrogenation, hydroxylation, alkyl hydroxylation, alcoholysis, hydrolysis, epoxidation, halogenation, sulfonation, oxidation, polymerization and combination thereof.In some embodiments, the oil of alkylation (comprise, such as, methylate and ethylize) is used.A kind of suitable modified natural oil is methylated soya oil.

The non-hydrocarbon ils of fat suitable equally is especially the self-emulsifying ester of fatty acid.

Another organizes suitable non-hydrocarbon ils is silicone oil.Silicone oil is partly or entirely connected oligomer or the polymer of the main chain that base is formed by-Si-O-for having.Silicone oil comprises, such as, and polydimethyl siloxane oil.Polydimethyl siloxane oil is oligomer or the polymer of unit containing following form:

Wherein at least one unit has X1=CH ₃.In other unit, X1 can be other group any that can be connected to Si, comprises, and such as, hydrogen, hydroxyl, alkyl, alkoxyl, hydroxyalkyl, hydroxyl alkoxyl, alkyl gather alkoxyl, its replacement form or its combination.Substituting group can comprise, and such as, hydroxyl, alkoxyl, polyethoxy, ether connect base, ester connects base, acid amides connects base, other substituting group or its any combination.In some embodiments, often kind of oil of use is silicone oil.

In the polydimethyl siloxane oil that some are suitable, all X1 groups are the group of non-hydrophilic.In the polydimethyl siloxane oil that some are suitable, all X1 groups are alkyl.In the polydimethyl siloxane oil that some are suitable, all X1 groups are methyl.In some embodiments, often kind of silicone oil is that wherein all X1 groups are the polydimethyl siloxane oil of methyl.In the dimethyl silicone polymer that some are suitable, at least one unit has the X1 group of non-methyl; If there is more than one non-methyl X1 unit, then this non-methyl X1 unit can be mutually the same, maybe can there is the non-methyl X1 unit that two or more are different.Polydimethyl siloxane oil can use any one end-blocking of number of chemical group, and described chemical group comprises, such as, and hydrogen, methyl, other alkyl or its any combination.Also X 2-1401 oil can be used.The mixture of suitable oil is also suitable.

Practice of the present invention comprises the particle be suspended in oily medium.Oil medium can be the application's any oil mentioned above." suspension " of the application represent particle be insoluble to or be only slightly soluble in oil and distribution of particles in whole oil, it forms continuous media around particle.The system being suspended in the particle in oil is called " suspension " in the application.Suspension of the present invention is stable; That is, under the standard conditions of 25 DEG C, 1 atmospheric pressure and normal gravity, after storage 1 day, most of particle (at least 80 % by weight, the gross dry weight based on particle) will be deposited to the bottom of container or float to container top.In some embodiments, based on the gross dry weight of particle, the amount being deposited to the particle of container bottom is after storage 10% or less, or 5% or less, or 2% or less, or 1% or less.Independently, in some embodiments, stable after storage 2 days or longer or 5 days or longer or 10 days or longer suspension is used in.

The aggregate of particle can be evaluated to determine size.A suitable evaluation method such as, is use microscope to check.The image of particle, such as, those images obtained in microscope, can by eye examination and assessment, possible reference length standard, or alternatively, image can by suitable image analysis method such as computer program inspection and assessment.

Particle is not in spherical embodiment wherein, usefully by the maximum gauge characterizing particles of each particle.The feature of aggregates body may be, maximum sized intermediate value.That is, the particle based on half in weight aggregate will have the full-size being greater than aggregate intermediate value.In the practice of the invention, when evaluating the aggregate of the particle be suspended in oily medium, this intermediate value is 50 microns or less.In some embodiments, intermediate value is used to be 20 microns or less; Or 10 microns or less; Or 5 microns or less; Or 2 microns or less particle.

The independent measure of particle is aspect ratio, and it is particle full-size and the ratio of particle minimum dimension.The size of aspect ratio and particle has nothing to do.In certain embodiments of the present invention, the aspect ratio being suspended in the aggregate of the particle in oily medium is 20 or lower; Or 10 or lower; Or 5 or lower; Or 2 or lower.

The particle be suspended in oily medium is solid.That is, particulate fraction or be made up of solid-state material completely.Each particle can be or can not be porous, or can have or one or more space can not be had, maybe can have or can not have one or more hole, each hole or space or hole (if existence) can or can not partially or completely be occupied by the material for solid, liquid or gas.The system being suspended in the particle in oily medium is synonymously called " dispersion ".

The particle be suspended in oily medium can comprise cyclopropylene and molecular encapsulation agent.In some embodiments, some or all being present in the cyclopropylene in composition are a part for cyclopropylene compound.Although the invention is not restricted to any particular theory or model, think be present in great majority in composition or all cyclopropene molecular exist using the molecular forms of the part as cyclopropylene compound.Think further, in composition for any cyclopropene molecular of a cyclopropylene compound part be present in such as solution, be adsorbed onto on interface, some other positions or its combination.In some embodiments, the amount of the cyclopropylene existed based on the part as cyclopropylene compound of cyclopropylene total amount in composition can be 80% or more; Or 90% or more; Or 95% or more; Or 99% or more.

In certain embodiments of the present invention, oily medium comprises one or more dispersants.Think, some or all of dispersant are dissolved in oil, and some or all of dispersant are positioned on particle surface (that is, the interface between particle and oily medium), or its combination.In addition, think, a small amount of dispersant (or not having) can be positioned at that one or more other is local, such as, in the surface of oil, on the wall, with the compound of molecular encapsulation agent, or its combination.

Application-defined " dispersant " to contribute to the compound that solid particle forms stable suspension in liquid medium.Most of dispersant works by making the ability of particle aggregation formation more possibility sedimentation (or becoming creaminess) remarkable larger particles minimize.In some embodiments, suitable dispersant has one or more hydrophilic radical.Independently, in some embodiments, suitable dispersant has multiple hydrophobic grouping.Some suitable hydrophobic groupings comprise, and such as, have the organic group of 8 or more continuous print carbon atoms.In some embodiments, the hydrophobic grouping of existence has 10 or more continuous print carbon atoms.Have nothing to do with carbon atom number, such organic group can be linear, ring-type, branching or its combination.Independently, such organic group can be hydrocarbon can be maybe replace.Independently, such organic group can be saturated or undersaturated.

Some suitable dispersant per molecules have 2 or more hydrophobic groupings, or 3 or more, or 4 or more or 5 or more.In some embodiments, often kind of dispersant per molecule has 4 or more hydrophobic groupings.In some embodiments, often kind of dispersant per molecule has 5 or more hydrophobic groupings.

Have nothing to do with the character of hydrophobic grouping, some suitable dispersants have one or more hydrophilic radical.Some suitable hydrophilic radicals comprise, such as, and the group that can ionize in water in the pH of certain limit, such as, carboxyl, sulfate groups, sulfonate group, and amine groups.Other suitable hydrophilic radical is non-ionic.Some suitable non-ionic hydrophilic groups comprise, such as, the following segment in polymer, if described segment exists independent of polymer, then water soluble.This hydrophilic segment of polymer comprises, such as, and polyethylene glycol segment.

Use wherein in the embodiment of dispersant, its molecule comprises hydrophobic grouping and at least one hydrophilic radical, and group can be connected to dispersant molecule by any means.Such as, some suitable dispersants are block copolymers, and this block copolymer has at least one block being polyethylene glycol segment and at least one comprises the block of multiple hydrophobic grouping.The example comprising the block of multiple hydrophobic grouping is the segment of poly-(12-hydroxy stearic acid).Another example comprising the block of multiple hydrophobic grouping is the segment of alkyd polymer.Alkyd polymer is the copolymer of polyalcohol, polyacid and fatty acid or triglyceride oil.

As used in this application, non-ionic dispersing agent is that wherein all hydrophilic radicals are non-ionic dispersant.In some embodiments, at least one non-ionic dispersing agent is used.In some embodiments, often kind of dispersant of use is non-ionic.

A kind of useful properties of nonionic molecule is HLB value, and it is defined by following equation

HLB＝20*M _H/M

Wherein M _hbe the molecular weight of the hydrophilic segment of molecule, M is the molecular weight of molecule.

Be no matter ion or non-ionic, the feature of useful molecule can be acid number (being synonymously called " acid number "), and it is for every gram of useful molecule, neutralizes the milligram number of the KOH needed for useful molecule.A kind of method of test acid number is shown in ASTM D-7253.Should be appreciated that, some details of test (such as, to the selection of solvent and/or indicator) can change for concrete useful molecule is necessary.

Use in some embodiments of one or more non-ionic dispersing agents wherein, the HLB of one or more dispersants is higher than 4, or HLB is 5 or higher.Independently, in some embodiments, the HLB of one or more dispersants of use is lower than 8, or HLB is 7 or lower.In some embodiments, the HLB of often kind of dispersant of use is 5 to 7.

Have nothing to do with the HLB value of dispersant, use in some embodiments of one or more non-ionic dispersing agents wherein, the unit of one or more dispersants is the acid number of mg KOH/g is 10 or lower; Or 9 or lower; Or 8 or lower.Independently, use in some embodiments of one or more non-ionic dispersing agents wherein, the unit of one or more dispersants is the acid number of mg KOH/g is 2 or higher; Or 4 or higher; Or 6 or higher.In some embodiments, the acid number of often kind of dispersant of use is 6 to 8mg KOH/g.

In some embodiments, the acid number of one or more dispersants of use is 6 to 8mg KOH/g or higher, and wherein the HLB of identical dispersant is also 5 to 7.

In some embodiments, one or more surfactants are used." surfactant " used in this application also represents the compound contributing to forming the stabilising dispersions of oil droplet in water with " emulsifier " synonym.The molecule of surfactant compounds comprises at least one hydrophilic radical and at least one hydrophobic grouping.Surfactant is usually according to the qualitative classification of hydrophilic radical.Suitable surfactant comprises, such as, anion surfactant, cationic surfactant, non-ionic surface active agent, amphoteric surfactant, and composition thereof.

Use wherein in the embodiment of one or more anion surfactants, some suitable anion surfactants comprise, such as, sulfosuccinate (comprises, such as, the basic salt of sulfosuccinic acid mono alkyl ester and dialkyl sulfosuccinate), sulphate, and sulfonate, comprise, such as, the basic salt of alkyl sodium sulfate ester.In some embodiments, anion surfactant is not used.

Use wherein in the embodiment of one or more cationic surfactants, some suitable cationic surfactants comprise, such as, and amine surfactant and quaternary surfactant.In some embodiments, cationic surfactant is not used.

In some embodiments, one or more non-ionic surface active agents are used.Use wherein in the embodiment of one or more non-ionic surface active agents, some suitable non-ionic surface active agents comprise, such as, fatty ethoxylate, the fatty acid ester of polyol compound, amide oxide, trialkylphosphine oxide block copolymer, based on organosilyl non-ionic surface active agent, fluorine-containing surfactant, and composition thereof.

Suitable fatty ethoxylate comprises, such as, and the ethoxylate of fatty alcohol, the ethoxylate of fatty acid, the ethoxylate of aliphatic ethanol amine, and the ethoxylate of fatty amine.The ethoxylate of suitable fatty alcohol comprises, and such as, has the ethoxylate of the fatty alcohol of any combination of following characteristics: straight chain or branching; Uncle or secondary; Alkyl or alkylaryl.In some embodiments, one or more fatty ethoxylate of use are aryl alkyl ethoxylates, alcohol ethoxylate, or its mixture.

Suitable comprises based on organosilyl non-ionic surface active agent, such as, has those of following formula

Wherein n is 1 to 5, m is 0 to 4, and Q is

Wherein p is 1 to 6, q is 3 to 20.In some embodiments, n is 1.Independently, in some embodiments, m is 0.Independently, in some embodiments, p is 3.Independently, in some embodiments, q is 7 or 8 or its mixture.A further example of suitable non-ionic surface active agent is Atplus 595.The mixture of suitable surfactant is also suitable.

The useful feature of non-ionic surface active agent can be HLB, as the application defines above.In some embodiments, the HLB of one or more non-ionic surface active agents of use is 3 to 4.Independently, in some embodiments, the HLB of one or more non-ionic surface active agents of use is 8 to 10.In some embodiments, use the mixture of surfactant, it comprise HLB be 3 to 4 one or more non-ionic surface active agents and HLB be 8 to 10 one or more non-ionic surface active agents.

In some embodiments (the application is called " continuously oil " embodiment), the continuous media of the present composition is the oily medium that particle suspends wherein.In some continuous oily embodiments, one or more surfactants are present in composition.In some continuous oily embodiments, surfactant is not had to be present in composition.Independently, in some continuous oily embodiments, exist and seldom or not there is water; That is, in such embodiment, if there is any water, then the amount based on the water of composition weight is 5 % by weight or less; Or 2 % by weight or less; Or 1 % by weight or less; Or 0.5 % by weight or less; Or 0.1 % by weight or less.

In some continuous oily embodiments, the amount of cyclopropylene is that 1 gram of cyclopropylene often rises oil (" g/L ") or more; Or 2g/L or more, or 5g/L or more, or 10g/L or more, or 20g/L or more.Independently, in some continuous oily embodiments, the amount of cyclopropylene is 200g/L or less; Or 100g/L or less; Or 50g/L or less.

In some continuous oily embodiments, the amount based on the dispersant of the weight of composition is 0.1 % by weight or more; Or 0.2 % by weight or more; Or 0.5 % by weight or more, or 0.75 % by weight or more.Independently, in some continuous oily embodiments, the amount based on the dispersant of the weight of composition is 20 % by weight or less; Or 10 % by weight or less; Or 5 % by weight or less; Or 2 % by weight or less.

In some continuous oily embodiments, the amount based on the surfactant of the weight of composition is 0.5 % by weight or more; Or 1 % by weight or more, or 2 % by weight or more.Independently, in some continuous oily embodiments, the amount based on the surfactant of the weight of composition is 20 % by weight or less; Or 10 % by weight or less.In some continuous oily embodiments, there is not surfactant.

In some continuous water embodiments, one or more surfactants are present in composition.In some continuous water embodiments, one or more non-ionic surface active agents are present in composition.In some continuous water embodiments, one or more HLB be 3 to 4 non-ionic surface active agent be present in composition, one or more HLB be 8 to 10 non-ionic surface active agent be also present in composition.In some embodiments, select one or more surfactants, because this surfactant is suitable for the drop emulsification making the concrete oil being used as oily medium in this embodiment well.

In some continuous water embodiments, the amount (based on weight) based on the cyclopropylene of the weight of composition is 10 parts every 1,000,000 parts (ppm) or larger; Or 20ppm or larger; Or 50ppm or larger.Independently, in some continuous water embodiments, the amount (based on weight) based on the cyclopropylene of the weight of composition is 500ppm or lower; Or 200ppm or lower.

In some continuous water embodiments, the amount (based on weight) based on the dispersant of the weight of composition is 2.5ppm or larger; 10ppm or larger; Or 50ppm or larger; Or 200ppm or larger.Independently, in some continuous water embodiments, the amount (based on weight) based on the dispersant of the weight of composition is 1250ppm or lower; Or 1000ppm or lower, or 750ppm or lower.

In some continuous water embodiments, based on the amount of the surfactant of the weight of composition, namely based on the dry weight of the surfactant of the weight of composition, be 0.02 % by weight or more, or 0.05 % by weight or more, or 0.1 % by weight or more, or 0.2 % by weight or more.Independently, in some continuous water embodiments, based on the amount of the surfactant of the weight of composition, namely based on the dry weight of the surfactant of the weight of composition, be 2 % by weight or less, or 1 % by weight or less, or 0.5 % by weight or less.

Composition of the present invention can be prepared by any method.In the method that some are suitable, starting material is oil, dispersant, optional surfactant, and cyclopropylene compound.In some embodiments, cyclopropylene compound starting material form be the powder particle comprising cyclopropylene compound, and the median particle diameter that powder particle is measured by full-size is much larger than 50 microns (such as, 200 microns or larger).In some embodiments, can starting material be put in medium grinder, then mill, until obtain desired particle size.In some embodiments, carry out milling technique, until particle is 50 microns or less by the median particle diameter that full-size is measured, or 20 microns or less, or 10 microns or less, or 5 microns or less, or 2 microns or less.

Relating in some embodiments of milling, based on the weight of the mixture of milling, the amount that the mixture of milling comprises cyclopropylene composite powder is 2 % by weight or larger; Or 5 % by weight or larger; Or 10 % by weight or larger; Or 20 % by weight or larger.Independently, relating in some embodiments of milling, based on the weight of the mixture of milling, the amount that the mixture of milling comprises cyclopropylene composite powder is 60 % by weight or lower; Or 50 % by weight or lower.

Relating in some embodiments of milling, based on the weight of the mixture of milling, the amount that the mixture of milling comprises dispersant is 0.02 % by weight or larger; Or 0.05 % by weight or larger; Or 0.1 % by weight or larger; Or 0.2 % by weight or larger; Or 0.5 % by weight or larger; Or 1 % by weight or larger.Independently, relating in some embodiments of milling, based on the weight of the mixture of milling, the amount that the mixture of milling comprises dispersant is 10 % by weight or lower; Or 7 % by weight or lower; Or 5 % by weight or lower.

Relating in some embodiments of milling, based on the weight of the mixture of milling, the amount that the mixture of milling comprises surfactant is 0.2 % by weight or larger; Or 0.5 % by weight or larger; Or 1 % by weight or larger.Independently, relating in some embodiments of milling, based on the weight of the mixture of milling, the amount that the mixture of milling comprises surfactant is 30 % by weight or lower; Or 10 % by weight or lower; Or 6 % by weight or lower.Relating in some embodiments of milling, the mixture of milling does not comprise surfactant.

Relating in some embodiments of milling, based on the weight of the mixture of milling, the amount that the mixture of milling comprises oil is 40 % by weight or larger; Or 50 % by weight or larger.Independently, relating in some embodiments of milling, based on the weight of the mixture of milling, the amount that the mixture of milling comprises oil is 98 % by weight or lower; Or 80 % by weight or lower; Or 70 % by weight or lower.

Relating in some embodiments of milling, water not included in starting material, not included in the mixture of milling, and not included in store time the mixture of milling not included in.That is, in such embodiment, based on the gross weight of starting material, in the mixture of starting material, the amount of water is 2 % by weight or less; Or 1 % by weight or less; Or 0.5 % by weight or less; Or 0.2 % by weight or less; Or 0.1 % by weight or less; Or 0.In such embodiment, in mill processes, mixture is considered to the water of identical amount, when storing mixture, the mixture of milling is considered to the water of identical amount.Compared with the mixture in mill processes, the mixture in storage process can contain or can not contain the water of higher amount.Independently, compared with the mixture of starting material before milling, the mixture in mill processes can contain or can not contain the water of higher amount.

The product of this technique of milling can use immediately and maybe can store.

When expecting to put into practice continuous oily embodiment, the product of technique of milling can directly use, or can add other oil to such mill in the product of technique.

When expecting to put into practice continuous water embodiment, the production sharing drop of such technique of milling is suspended in water-bearing media.In some embodiments, the product of technique of milling can be added in water-bearing media and to make it experience stirring, and by drop that the production sharing of technique of milling suspends.In some such embodiments, select one or more surfactants separate with the product of the technique that contributes to milling and be suspended in water-bearing media, one or more such surfactants to be added in starting material and to be included in the mixture of milling.No matter whether surfactant is included in the mixture of milling, one or more surfactants can be added to after completing technique of milling and mill in the product of technique, or add in water-bearing media (before or after by the Product mix of water-bearing media and technique of milling).

Usually, whenever using cyclopropylene compound, the direct contact between known cyclopropylene compound and water causes cyclopropylene from the morning needed for the release ratio compound sometimes, and cyclopropylene possible loss (such as, diffused out by composition, by chemical reaction, or its combination).Think in the practice of continuous water embodiment of the present invention, cyclopropylene compound is retained in oily medium, make the contact between cyclopropylene compound and water minimize or eliminate thus, the cyclopropene molecular of the high score rate of the therefore expectation of composition retains in the composition.

The one of the present composition may purposes be process plant or plant part by making composition of the present invention contact with plant or plant part.The plant producing useful plant part is called " crop plants " in the application.Can on growing plant or from growing plant harvesting the enterprising row relax of plant part.Think, when the enterprising row relax of growing plant, composition of the present invention with whole plant contact or can contact with one or more plant part.Plant part comprises any part of plant, and such as, flower, bud, view and admire flower (blooms), seed, transplants, root, stem, fruit, vegetables, leaf, and combination.

Take off useful plant part from crop plants and be called harvesting.In some embodiments, before the plant part that harvesting is useful, with compositions-treated crop plants of the present invention.

Composition of the present invention can contact with plant or plant part by any method, and described method comprises, such as, and spraying, dipping, spray, atomization, and combination.In some embodiments, spraying is used.

Suitable process can be carried out on plant, and described plant is in field, in park, in building (such as, greenhouse) or plant in another position.Suitable process can be carried out on following plant, described planting on the soil opened wide, be planted in one or more container (such as, tank, planter, or vase), be planted in limited bed or implant bed or be planted in other position.In some embodiments, at the enterprising row relax of the plant being positioned at other position except building.In some embodiments, when plant also during growth, processes plant in container (such as, tank, tray, or Portable bed).

Usefully a lot of plants being applicable to the present invention's practice can be divided into kind or group.A kind of process useful limiting such group is " Definition and Classification of Commodities ", the same day on March 23rd, 2006 or before deliver, " first draft " formulated by Food and Agricultural Organization of the United Nations (" FAO ").

In the practice of some embodiments of the present invention, the plant producing the crop of following crop group within the scope of any one can be used.

Crop group 1 is cereal, comprises, such as, and wheat, rice, barley, corn, popcorn (popcorn), rye, oat, millet, Chinese sorghum, buckwheat, lamb's-quarters wheat (quiona), Fu Niao meter (fonio), triticale, sparrow grain (canary seed), melon river crop (canagua) received by card, aloe tea (quihuicha), Job's tears, wild rice, and other cereal.In certain embodiments of the present invention, suitable plant produces those of wheat or rice or corn or Chinese sorghum.In some embodiments, crop plants is suitable.In some embodiments, wheat plant is suitable.Crop group 2 is root and stem tuber.

Crop group 3 is sugar crops, comprises, such as, and sugarcane, beet, sugar maple, sugar grass, gomuti palm (sugar palm), and other sugar crops.Crop group 4 is beans, comprises, such as, and Kidney bean, chickpea, triangle beans (garbanzo), cowpea (blackeyed pea), pigeonpea, lentil, and other beans.Crop group 5 is nuts, comprises, such as, and Bertholletia excelsa, cashew nut, chestnut, almond, English walnut, pistachio, fibert, pecan, macadamia, and other nut.

Crop group 6 is oil-containing crops, comprises, such as, and soybean, peanut (comprising peanut), coconut, oil palm fruit, olive, card Z-TEK tree nut (karite nuts), castor bean, sunflower seed, rape seed, canola, tung nut, Semen Carthami, sesame seed, mustard seeds, poppy seed, muskmelon seeds, Chinese tallowtree seed (tallowtree seeds), baobab (kapok fruit), unginned cotton, linseed, hempseed, and other oilseed.In some embodiments, bean plant is suitable.

Crop group 7 is vegetables, comprise, such as, cabbage, artichoke, asparagus, lettuce, spinach, cassava leaves (cassava leaves), tomato, cauliflower, pumpkin, cucumber and cuke, eggplant, red pepper and pepper, shallot, dry onion (dry onions), garlic, leek, other allium vegetables, kidney bean, green pea, green broad bean, green soya bean, carrot, okra, greenstone rice (green corn), mushroom, watermelon, cantaloupe (cantaloupe melons), bamboo shoots, beet root (beets), edible beet (chards), caper, cardoon, celery, chervil, Chinese celery, fennel, horseradish, matchmaker's ink angle is blue, salsify, celery, parsnip, radish, rheum officinale, winter rape, savoury, crow green onion, sorrel, watercress, with other vegetables.

Crop group 8 is fruit, comprises, such as, and banana and Asiatic plantain; Citrus fruit; Pomaceous fruits fruit; Drupe; Berry; Tendril fruit; Tropical fruit (tree); Mix fruit (miscellaneous fruits); With other fruit.Crop group 9 is fiber-like, comprises, such as, and cotton, flax, hemp, common bombax flower, jute, ramie, sisal hemp, and other fiber-like plant.In some embodiments, vegetable lamb is suitable.Crop group 10 is perfumeries.Crop group 11 is forage crop.Forage crop is the crop of cultivating mainly for animal feeding.Crop group 12 is excitant crops, comprises, such as, coffee, cocoa bean, tea, companion's thing (mate), for the preparation of soak other plant as tea, and other excitant crop.

Crop group 13 is tobacco and rubber and other crop, comprises, such as, for the vegetable oil of perfumery, food and other industry, and Dalmatian chrysanthemum, tobacco, natural rubber, natural gum, other resin, and vegetable wax.

In some embodiments, the present invention includes any non-citrus of process (that is, any plant of non-Citrus).In other embodiments, practice of the present invention is limited to the non-citrus of process.Independently, in some embodiments, all plants of process are not the members of Nicotiana.

In some embodiments, composition of the present invention is for the treatment of the crop plants grown in field.Such process operation can be carried out once or more than once in single Growing season process on other crop plants of particular group.In some embodiments, the amount for the cyclopropylene of single treatment is 0.1 gram of per hectare (g/ha) or more; Or 0.5g/ha or more; Or 1g/ha or more; Or 5g/ha or more; Or 25g/ha or more; Or 50g/ha or more; Or 100g/ha or more.Independently, in some embodiments, the amount for the cyclopropylene of a spray operation is 6000g/ha or less; Or 3000g/ha or less; Or 1500g/ha or less.Also the embodiment of the plant part wherein processing harvesting can be used.

In some embodiments, composition of the present invention comprises one or more metal chelating agents.Metal chelating agent comprises one or more compound that can form the electron donor atom of coordinate bond with metallic atom.Some metal chelating agents are chelating agents." chelating agent " used in this application comprises two or more can form the electron donor atom of coordinate bond compound with metallic atom, and the individual molecule of chelating agent can form two or more coordinate bonds with single metal atom.In some embodiments, one or more chelating agents are used.In some embodiments, not using is not the metal chelating agent of chelating agent.

Use wherein in the embodiment of one or more chelating agents, suitable chelating agent comprises, such as, and organic and inorganic chelator.Suitable inorganic chelator especially, such as, phosphate, such as, tetrasodium pyrophosphate, sodium phosphate trimer, and hexa metaphosphoric acid.Suitable organic sequestering agent especially has those of macrocyclic structure and non-macrocyclic structure.

Some suitable organic sequestering agents with non-macrocyclic structure are, such as, amino carboxylic acid, 1,3-diketone, hydroxycarboxylic acid, polyamines, amino alcohol, aromatic heterocycle alkali, phenol, amino phenols, oxime, Shiff alkali, sulphur compound, and composition thereof.In some embodiments, chelating agent comprises one or more amino carboxylic acids, one or more hydroxycarboxylic acids, one or more oximes, or its mixture.Some suitable amino carboxylic acids comprise, such as, ethylenediamine tetra-acetic acid (EDTA), Oxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), N-dihydroxyethylglycin (2-HxG), ethylene (hydroxyphenyl) (EHPG), and composition thereof.Some suitable hydroxycarboxylic acids comprise, such as, tartaric acid, citric acid, gluconic acid, 5-sulphosalicylic acid, and composition thereof.Some suitable oximes comprise, such as, dimethylglyoxime, salicylaldoxime, and composition thereof.In some embodiments, EDTA is used.

Metal chelating agent is optional use in the present invention.In some continuous water embodiments, use one or more metal chelating agents.In some continuous water embodiments, do not use metal chelating agent.In some continuous oily embodiments, do not use metal chelating agent.

Also should be understood that the object for specification of the present invention and claims, unless expressly stated otherwise, otherwise when stating that numerical value be " from X to Y ", showing that this numerical value is X or larger and be Y or less.

Should understand, for the object of specification of the present invention and claims, unless expressly stated otherwise, otherwise when compound being described as the result of specified chemical reaction, such description is intended to the structure describing compound, and prepares by carrying out the reaction of this specified chemical regardless of whether compound is actual.Such as, " ethoxylate of fatty alcohol " is that its structure can by imagining the compound carrying out ethoxylation to understand on fatty alcohol, and such compound by the ethoxylation process preparation of fatty alcohol or can be prepared by diverse ways.

Should be understood that the object for specification of the present invention and claims, unless expressly stated otherwise, otherwise operate in 25 DEG C of aerial atmospheric pressure and carry out.

Should be understood that the object for specification of the present invention and claims, scope the application can stated and the combination of ratio boundary.Such as, if set forth the scope of 60 to 120 and 80 to 110 for special parameter, then the scope that also can use 60 to 110 and 80 to 120 should be understood.As independently example further, if the suitable minimum of a value that open special parameter has is 1,2 and 3, and if disclose this parameter, to have suitable maximum be 9 and 10, then can use all following scopes: 1 to 9,1 to 10,2 to 9,2 to 10,3 to 9, and 3 to 10.

The thickener that can be mixed in the suspension composition provided comprises thickening or increases those components of composition viscosity.The thickener that may be used for the suspension composition provided is included in those components that this area is called viscosity-control additive.

The example of thickener comprises such as, based on cellulosic thickener, hydroxy ethyl cellulose, methylcellulose, hydroxy propyl cellulose and carboxy methyl cellulose.Other example of thickener comprises cellulose gum, alkane triol; Acrylate; The cellulose replaced, such as hydroxy ethyl cellulose, carboxy methyl cellulose, methylcellulose, and hydroxy propyl cellulose; Cetyl alcohol; Glue, such as natural gum or rubber polymer; Long-chain alcohol, such as, have those of about 9 to about 24 carbon atoms; Polyglycols, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-ethylene propylene glycol, or its mixture; Wax, such as native paraffin or synthetic wax; Hydrogenated oil and fat; Diol ester; Fatty acid ester; Long chain acid; Acid acid amides; Silicate; And composition thereof.Thickener suitable in addition comprises organic clay, and it can be prepared by making hydrophilic clay and quaternary ammonium compound react by natural terre verte, hectorite or montmorillonitic clay, and it becomes organophilic thus, therefore compatible with non-aqueous media.

In one embodiment, suitable thickener comprises polymer viscosifier, and it is the addition polymer of unsaturated carboxylic acid and/or acid anhydride.The example of polymer viscosifier comprises polyacrylate, polyalkyl acrylate, polymethacrylates, and maleic anhydride.The mean molecule quantity of these polymer viscosifiers can be about 500,000 to about 200 ten thousand; Or 100 ten thousand to 4 hundred ten thousand.

In another embodiment, suitable thickener comprises the copolymer of acrylate and methacrylate, or the copolymer of acrylic acid and alkyl methacrylate, such as, be disclosed in United States Patent (USP) 5,373,044 and the U.S. disclosed application US2009/0253862A, its content is by reference to being incorporated to the application.The viscosity of the suspension composition provided can be about 50 to about 50,000mPas; Or 500 to 15,000mPas.

Suitable polymer viscosifier can be selected from natural rubber, polypropylene, polyisoprene, polybutadiene, poly-(styrene-butadiene), poly-(Ethylene-Propylene-Diene), polyurethane, polymethacrylates, polyisobutene, poly-(isobutene-succinic acid), poly-(isobutene-succinic acid-polyacrylamide), polyureas and polyethylene.In some embodiments, polymer viscosifier comprises the first component and second component, and wherein the weight average molecular weight of the first component is higher than the weight average molecular weight of second component.Such as, polymer viscosifier comprises high molecular weight component and lower-molecular-weight component, be characterised in that thickener comprises the mixture of following component: (1) weight average molecular weight is greater than (copolymerization or homopolymerization) polymer of the propylene of 200.000, and (2) weight average molecular weight is less than (copolymerization or homopolymerization) polymer of the propylene of 200.000.

In another embodiment, polymer viscosifier comprises: high molecular weight component, and it comprises (copolymerization or homopolymerization) polymer of propylene that weight average molecular weight is at least 200.000 or 200.000-350.000; And lower-molecular-weight component, it comprises weight average molecular weight and is less than 100.000 or (copolymerization or homopolymerization) polymer of propylene for 50.000-100.000.In polymer viscosifier, the weight ratio of high molecular weight component and lower-molecular-weight component can be 1:40-3:1; 1:40-1:1; 1:40-1:5; 1:25-1:15; Or 1:18-1:20.

In one embodiment, lower-molecular-weight component comprises polypropylene homopolymer, or is the polypropylene homopolymer of 500-1500dg/min. or 750-1250dg/min. by the melt flow rate (MFR) that test ASTM D 1238L measures.In further or interchangeable embodiment, lower-molecular-weight component comprises polypropylene homopolymer.In another embodiment, the melt flow rate (MFR) (ASTM D-1238) of high molecular weight component is 1.5-15; 1.5-7; Or 3-5.In further or interchangeable embodiment, high molecular weight component comprises polypropylene homopolymer or propylene/ethylene copolymer.

On the other hand, provide the composition of bag oil containing medium, wherein particle is suspended in described oily medium, and wherein said particle comprises cyclopropylene and molecular encapsulation agent, and wherein said particle is 50 microns or less by the median particle diameter that full-size is measured.

In one embodiment, described oily medium comprises one or more dispersants.In another embodiment, described oily medium comprises one or more non-ionic surface active agents.In another embodiment, described oily medium comprise one or more HLB value be 3 to 4 non-ionic surface active agent and one or more HLB value be the non-ionic surface active agent of 8 to 10.In another embodiment, the form of described oily medium is the drop be suspended in water.In another embodiment, described oily medium forms the continuous media of described composition.In another embodiment, the median aspect ratio of described particle is 20 or less.

On the other hand, this application provides the method for process plant or plant part, comprising: the composition that the application is provided contacts with described plant or plant part.On the other hand, this application provides the method forming composition, described method comprises: preparation comprises the mixture of cyclopropylene compound, oil and dispersant, puts in medium grinder; With described mixture of milling to form the particle comprising described cyclopropylene compound, wherein said particle is 300 microns or less by the median particle diameter that full-size is measured, 200 microns or less, or 50 microns or less.

On the other hand, this application provides the composition of the solid particle comprising cyclopropylene compound, described cyclopropylene compound comprises the part being encapsulated in cyclopropene molecular in molecular encapsulation agent or cyclopropene molecular, be characterised in that the other bag oil containing medium of described composition, described solid particle is suspended in described oily medium, and described solid particle is 50 microns or less by the median particle diameter that full-size is measured.

In one embodiment, described oily medium comprises one or more dispersants.In another embodiment, described molecular encapsulation agent is alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, or its mixture.In another embodiment, described cyclopropene molecular has the structure of following formula

In further embodiment, R is C _1-8alkyl.In another embodiment, R is methyl.

In another embodiment, described cyclopropene molecular has the structure of following formula:

Wherein R ¹substituted 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 ⁴hydrogen.In further embodiment, cyclopropylene comprises 1-methyl cyclopropene (1-MCP).

In another embodiment, described oily medium comprises one or more non-ionic surface active agents.In another embodiment, described oily medium comprise one or more HLB value be 3 to 4 non-ionic surface active agent and one or more HLB value be the non-ionic surface active agent of 8 to 10.In another embodiment, the form of described oily medium is the drop be suspended in water.In another embodiment, described oily medium forms the continuous media of described composition.In another embodiment, the median aspect ratio of described particle is 20 or less.

Embodiment

Material for following examples is these:

Compound 1=comprises the dried powder of the compound of 1-MCP and alpha-cyclodextrin, and it comprises the 1-MCP of 3.8 % by weight.The median particle diameter measured by longest dimension is greater than 100 microns.Median aspect ratio is greater than 50.

Oil P1=comprises the paraffin oil of aryl alkyl alcohol ethoxylate surfactant, derives from WhitmireMicro-Gen Company

Oil P2=paraffin oil, derives from Petro Canada Company

Brij ^tM30=surfactant: (oxirane) ₄lauryl ether, derives from Croda (HLB 9.7)

Silwet ^tMl-77=surfactant: non-ionic silicone, derives from OSi Specialties (HLB 5 to 8)

Atlox ^tM4914=dispersant: the block copolymer of poly-(oxirane) and alkyd resins, derives from Croda (HLB 6)

EDTA=ethylenediamine tetra-acetic acid, sodium salt

Atsurf ^tM595=surfactant: ethylene glycol monoleate, derives from Croda Company (HLB3.8)

Dyne-Amic ^tMoil=highly refined methylated vegetable oils and the blend combined based on organosilyl surfactant, derive from Helena Chemicals

Fat liquor 1=is by 0.38 weight portion Dyne-Amic ^tMoil adds in 99.62 weight parts waters, and stirs

Rizo ^tMoil=emulsible methylated soya oil, derives from Rizo bacter Company

SoyGold ^tM1100=methylated soya oil, derives from Ag Environmental ProductsCompany

Embodiment 1

Form preparation B

Following composition is added in medium grinder:

292.4g oily P1

102.0g compound 1

The Atlox of 5.6g ^tM4914

The mixture of each composition is processed in medium grinder, until the median particle diameter measured by full-size is less than 2 microns.

Embodiment 2

Form formulation C

Following composition is added in medium grinder:

194.2g oily P2

175.0g compound 1

The Brij of 6.0g ^tM30

18.0g Silwet ^tMl-77

The Atlox of 6.8g ^tM4914

Embodiment 3

Form preparation D

Following composition is added in medium grinder:

200.4g SoyGold 1100

180.0g compound 1

10.0g Silwet ^tMl-77

The Atlox of 4.0g ^tM4914

The EDTA of 5.6g

Embodiment 4

The reservation of 1-MCP

The ability that preparation retains 1-MCP is evaluated as follows: sprayed by spraying mixture by standard spray mouth, at spray nozzle place with collecting spraying liquid from nozzle 46cm (18 inches) place, and by the liquid that obtains the collection in closed container with analyze 1-MCP by gas chromatographic analysis headspace gas.The gas-chromatography of headroom is carried out according to described in U.S. Patent Publication 2005/0261132.Also initial and final non-blowing portion is analyzed to determine to be lost in the amount of spraying and be lost in the amount of headroom in spray operation process.

Spray agent " contrast SF-A4 " is the mixture of fat liquor 1 and compound 1.Spray agent " SF-B4 " is the preparation B added in water.The 1-MCP of each self-contained 100mg/L of spray agent is also sprayed at 138kPa (20psi) pressure and is passed through TeeJet ^tMxR8002VS nozzle.The results are shown in table 1:

Table 1 shows, and the performance of oil formulation is much better than the tank mixture of 1-MCP compound and oil, and in the spraying liquid also contributing to that 1-MCP is remained on and do not spray.

Embodiment 5

Biological effectiveness

Effect of preparation is evaluated as follows: to greenhouse tomato plant spray, makes them be exposed to ethene, and evaluates the tolerance responded the clear and definite epinasty (that is, bending blade/curling) caused by ethene.

The plant of 1-MCP process and contrast are put into SLX controls-air canister sealing.In case, inject ethene by barrier film, obtain the concentration of 14ppm.Plant is made to keep in the dark in an atmosphere sealing 12-14 hour together with ethene.At the end of ethene process, case is opened, carry out marking to the epinasty of plant.Result is offered as the leaf angle relative to stem, and wherein the value of 50 degree is typical impregnable leaf, and 120 degree is completely bending those due to the effect of ethene.

Spray agent " contrast SF-A51 " is 99.99 weight portion fat liquor 1 and 0.0132 weight portion compounds 1.Contrast SF-A2 is sprayed on plant, obtains the rate of application of 1g 1-MCP/Ha.Spray agent " contrast SF-A52 " is 99.17 weight portion fat liquor 1 and 0.132 weight portion compounds 1.Contrast SF-A2 is sprayed on plant, obtains the rate of application of 10g 1-MCP/Ha.

Spray agent " " SF-C51 " be 0.0279 weight portion formulation C and 99.97 weight parts waters.SF-C51 is sprayed on plant, obtains the rate of application of 1g 1-MCP/Ha.Spray agent " SF-C52 " is 0.279 weight portion formulation C and 99.72 weight parts waters.SF-C52 is sprayed on plant, obtains the rate of application of 10g 1-MCP/Ha.

Leaf angle proves, compared with Comparative formulation, it is comparatively effective that oil formulation SF-C51 and SF-C52 offsets Ethylene influences aspect.

Embodiment 6

Crop yield increases

On soybean, effect of preparation is evaluated in field is used.Measuring as output increases of effect.

Spray agent " contrast SF-A6 " is prepared as follows.By 98.97 weight parts waters in aerosol can with 1 weight portion Rizo ^tMoil mixing, then makes 0.0329 weight portion compound 1 mix in aerosol can with mixture.Select spraying rate to obtain comprising 2L/Ha of Rizo ^tM25g1-MCP/Ha in the 200L/Ha water of oil.By ground level spray application contrast SF-A6.

Sprayable preparation SF-D6 passes through 1.25 liters of preparation D and 3.75 liter Rizo ^tMoil is mixed with.Sprayable preparation SF-D6 is by using with the rate of application aerial spraying of the 25g 1-MCP/Ha in the total oil/Ha of 5L.Attention: do not use water in SF-D6

, therefore total liquid spray volume is 5L/Ha.The results are shown in table 3.Output is reported as the percentage of the output deriving from untreated contrast.

Compared with Comparative formulation, SF-D6 increases soybean yields more significantly.

Embodiment 7

Comprise the suspension composition of Kraton G1702H

Kraton G1702H is line style styrene ethylene/propylene diblock copolymer.The Isopar V of Kraton G1702H and the 1900g of 100g is mixed, and is under agitation heated to 100 DEG C and keeps 30 minutes.The viscous liquid of clarification is defined with 5% solid.

Similarly, more but viscosity still dumpable liquid can be formed by the concentration of 8%Kraton G1702H in Isopar V.These concentrated solution can dilute by simply mixing in room temperature with other solvent.

Useful especially viscosity is found in: in a solvent 2.25% Kraton G1702H and in a solvent 2.50% Kraton G1702H.Kraton G1702H also can be dissolved in (1) white mineral oil by similar concentration, comprise Blandol and Klearol; (2) hydrotreated middle petroleum distillate, comprises Conosol260, Unipar SH 260CC, Isopar V Fluid; (3) hydrotreated light petroleum fraction, such as Unipar SH 210AS, Isopar M Fluid.Above composition can obtain having the solution increasing viscosity separately.Vegetable oil (comprising soybean oil and corn oil) does not show this effect.When 1-methyl cyclopropene/alpha-cyclodextrin compound and/or zeolite/molecular sieve are suspended in the hydrocarbon of thickening, if the concentration of Kraton G1702H is greater than 2.0 % by weight, then there is few sedimentation or sedimentation do not occur.And the 1-methyl cyclopropene/alpha-cyclodextrin compound of 10 % by weight and the suspension of the Siliporite NK10AP (4A molecular sieve) of 3.3 % by weight in 2.25%Kraton G1702H use the normal pressure of 30psig to 60psig to carry out Direct spraying by using traditional spray mouth (spraying system TeeJet XR8002 or XR8008).

The polymer be not suitable for as thickener comprises: (1) Nordel IP3745P-ethylene, propylene norbornadiene terpolymer: mixed by the Isopar V of Nordel IP3745 and the 1900g of 100g, and be under agitation heated to 100 DEG C and keep 4 hours.Notice, seem not dissolve also there is no thickening; (2) Septon 1020-line style styrene ethylene/propylene diblock copolymer: the Septon 1020 of 100g is mixed with the Isopar V of 1900g, and be under agitation heated to 100 DEG C and keep 4 hours.Notice, only fraction dissolves, but only smaller portions thickening; (3) Septon 1001-line style styrene ethylene/propylene diblock copolymer: the Septon 1001 of 100g is mixed with the Isopar V of 1900g, and be under agitation heated to 100 DEG C and keep 4 hours.Notice, only fraction dissolves, but some (but insufficient) thickenings.

Claims

1. a composition, its bag oil containing medium and at least one thickener,

Wherein said composition is the suspension of solid particle in described oily medium, and described solid particle comprises compound cyclopropene and molecular encapsulation agent.

2. the composition of claim 1, wherein said suspension does not precipitate and reached at least two weeks.

3. the composition of claim 1, wherein said oily medium is selected from white mineral oil, hydrotreated middle petroleum distillate, hydrotreated light petroleum fraction, and combination.

4. the composition of claim 3, wherein said white mineral oil comprises Blandol and/or Klearol.

5. the composition of claim 3, wherein said hydrotreated middle petroleum distillate comprises Conosol 260, Unipar SH 260CC, and/or Isopar V.

6. the composition of claim 3, wherein said hydrotreated light petroleum fraction comprises UniparSH 210AS and/or Isopar M.

7. the composition of claim 1, wherein said compound cyclopropene has following formula:

8. the composition of claim 7, wherein R is C _1-8alkyl.

9. the composition of claim 7, wherein R is methyl.

10. the composition of claim 1, wherein said compound cyclopropene has following formula:

The composition of 11. claims 1, wherein said compound cyclopropene comprises 1-methyl cyclopropene (1-MCP).

The composition of 12. claims 1, wherein said molecular encapsulation agent is selected from the cyclodextrin of replacement, unsubstituted cyclodextrin, and combination.

The composition of 13. claims 1, wherein said molecular encapsulation agent comprises alpha-cyclodextrin.

The composition of 14. claims 1, wherein said solid particle accounts at least 10 % by weight of described composition.

The composition of 15. claims 1, wherein said composition comprises the 1-methyl cyclopropene (1-MCP) of at least 10 % by weight and the compound of alpha-cyclodextrin.

The composition of 16. claims 1, wherein said composition comprises the described at least one thickener of at least 1 % by weight.

The composition of 17. claims 1, wherein said at least one thickener comprises based on cellulosic thickener.

The composition of 18. claims 1, wherein said at least one thickener comprises polymer viscosifier.

The composition of 19. claims 18, wherein said polymer viscosifier is formed by least one in acrylate, alkyl acrylate and acid anhydride.

The composition of 20. claims 18, wherein said polymer viscosifier comprises at least one and is selected from following component: polypropylene, polyisoprene, polybutadiene, poly-(styrene-butadiene), poly-(styrene-ethylene/propylene), poly-(Ethylene-Propylene-Diene), polyurethane, polymethacrylates, polyisobutene, poly-(isobutene-succinic acid), poly-(isobutene-succinic acid-polyacrylamide), polyureas, polyethylene, and combination.

The composition of 21. claims 18, wherein said polymer viscosifier comprises the first component and second component, and wherein the weight average molecular weight of the first component is higher than the weight average molecular weight of second component.

The composition of 22. claims 21, wherein the weight ratio of the first component and second component is at least 1:5.

The composition of 23. claims 21, wherein said polymer viscosifier does not comprise ethylene, propylene norbornadiene copolymer.

The composition of 24. claims 21, wherein said polymer viscosifier does not comprise styrene ethylene/propylene copolymer.

The method of 25. supending compositions, comprising:

A material is put in medium grinder by (), described material comprises the compound of cyclopropylene and molecular encapsulation agent, oily medium and at least one thickener; With

B described material is ground to form the composition comprising solid particle by ().

The method of 26. claims 25, wherein said suspension composition does not precipitate and reached at least two weeks.

The method of 27. claims 25, wherein said cyclopropylene comprises 1-methyl cyclopropene (1-MCP).

The method of 28. claims 25, wherein said molecular encapsulation agent is selected from the cyclodextrin of replacement, unsubstituted cyclodextrin, and combination.

The method of 29. claims 25, wherein said molecular encapsulation agent comprises alpha-cyclodextrin.

The method of 30. claims 25, wherein said solid particle accounts at least 10 % by weight of described composition.

The method of 31. claims 25, wherein said composition comprises the 1-methyl cyclopropene (1-MCP) of at least 10 % by weight and the compound of alpha-cyclodextrin.