JP2015530474A - Oil formulation with thickener - Google Patents

Abstract

The present invention is based on the unexpected effect of at least one thickener to maintain the suspension or dispersion of solid particles in an oil medium. Such an effect of the thickener allows a significantly greater weight ratio of solid particles in such a suspension composition compared to previously known compositions. As a result, the suspension compositions provided herein have more active ingredients in solid particles present in a constant volume or weight of the composition as compared to previously known compositions. Make it possible. One advantage of the suspension compositions provided herein is possible for aerial application of active ingredients such as herbicides, insecticides or other growth regulating compounds.

Description

This application claims priority to US Provisional Patent Application No. 61 / 710,019 (filed Oct. 5, 2012) under 35 USC 119 (e), the disclosure of which is express Which is incorporated herein by reference).

  In order to use a cyclopropene compound, the cyclopropene compound is often in the form of a complex with a molecular encapsulating agent. Such complexes are for example used in treating a plant or plant part by contacting the plant or plant part with such a complex to provide contact between the plant or plant part and the cyclopropene compound. Useful for. Such treatment of plants or plant parts is often effective in desirably interrupting one or more ethylene-mediated processes in the plant or plant part. For example, such treatment of plant parts can sometimes desirably delay ripening undesirably. As another example, such treatment of crop plants before harvest can sometimes improve crop yield.

  US Pat. No. 6,313,068 discloses grinding and milling of a dried powder of a complex of cyclodextrin and methylcyclopropene.

  It is often useful to dissolve or suspend such complex particles in a liquid. However, if the water is such a liquid, contact of the water with the particles of the complex will cause the release of the cyclopropene compound from the complex faster than desired, and thus a portion of the cyclopropene compound. Or it is sometimes found that everything is lost to the surrounding environment or destroyed by chemical reactions or combinations thereof. Therefore, it is often desirable to suspend such particles in oil. However, in the past, various attempts to suspend such particles in oil have been found that such particles could not be effectively suspended in oil. This is often because the suspension could not be sprayed properly, or because the suspension had too much viscosity at a reasonable concentration of particles, or the suspension was stable. Not because the suspension settled and creamed, or because the suspension had some combination of these problems. It is an object of the present invention to provide a suspension in oil of particles containing a cyclopropene complex that solves one or more of these problems.

US Pat. No. 6,313,068

  The present invention is based on the unexpected effect of at least one thickener to maintain the suspension or dispersion of solid particles in an oil medium. Such an effect of the thickener allows a significantly greater weight ratio of solid particles in such a suspension composition compared to previously known compositions. As a result, the suspension compositions provided herein have more active ingredients in solid particles present in a constant volume or weight of the composition as compared to previously known compositions. Make it possible. One advantage of the suspension compositions provided herein is possible for aerial application of active ingredients such as herbicides, insecticides or growth regulating compounds. Other advantages of the suspension compositions provided herein include sustained release of cyclopropene and less payload weight for airplanes and helicopters for aerial application.

  Suspensions of cyclopropene / cyclodextrin complexes in hydrophobic fluids with adjuvants are provided that can form a system for controlled delivery of cyclopropene compounds.

  In one embodiment, a composition comprising an oil medium and at least one thickener, wherein the composition is a suspension of solid particles in the oil medium, and the solid particles are cyclopropene and molecular encapsulation. A composition comprising an agent is provided.

  In one embodiment, the suspension does not settle for at least 2 weeks, at least 4 weeks, at least 8 weeks, at least 20 weeks or at least 40 weeks. In another embodiment, the oil medium is selected from the group consisting of white mineral oil, hydrotreated intermediate petroleum distillate, hydrotreated light petroleum distillate, and combinations thereof. In a further embodiment, the white mineral oil comprises Blandol and / or Klearol. In another further embodiment, the hydrotreated intermediate petroleum distillate comprises Conosol 260, Unipar SH 260CC, and / or Isopar V. In another further embodiment, the hydrotreated light petroleum distillate comprises Unipar SH 210AS and / or Isopar M.

In one embodiment, the cyclopropene compound is of the formula:

Wherein R is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkylalkyl group, phenyl group or naphthyl group; the substituent is independently halogen, alkoxy Or substituted or unsubstituted phenoxy.

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

In another embodiment, the cyclopropene compound is of the formula:

In the formula, R ¹ is a substituted or unsubstituted C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkenyl group, C ₁ -C ₄ alkynyl group, C ₁ -C ₄ cycloalkyl group, cycloalkylalkyl. A group, a phenyl group or a naphthyl group, and R ² , R ³ and R ⁴ are hydrogen.

  In one embodiment, the cyclopropene comprises 1-methylcyclopropene (1-MCP). In another embodiment, the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, and combinations thereof. In a further embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin.

  In one embodiment, the solid particles comprise at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50% or at least 60% by weight of the composition. Configure. In another embodiment, the solid particles are 10% to 20%, 10% to 30%, 10% to 40%, 10% to 50%, 10% by weight of the composition. -60 wt%, 20 wt% to 40 wt%, 30 wt% to 60 wt%, or 40 wt% to 60 wt%. In another embodiment, the composition comprises at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50% or at least 60% by weight of 1-methyl. It includes a complex of cyclopropene (1-MCP) and alpha-cyclodextrin. In another embodiment, the composition is 10% to 20%, 10% to 30%, 10% to 40%, 10% to 50%, 10% to 60% by weight. 20% to 40%, 30% to 60%, or 40% to 60% by weight of a complex of 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin.

  In one embodiment, the composition comprises at least 1 wt%, at least 3 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least one thickener. 30% by weight, at least 40% by weight or at least 50% by weight. In another embodiment, the composition comprises 1% to 20%, 1% to 30%, 1% to 40%, 1% to 50% by weight of the at least one thickener. 5 wt% to 20 wt%, 5 wt% to 40 wt%, 10 wt% to 50 wt%, or 20 wt% to 50 wt%. In another embodiment, the at least one thickener comprises a cellulosic thickener. In another embodiment, the at least one thickener comprises a polymeric thickener. In a further embodiment, the polymeric thickener is formed from at least one of an acrylate, an alkyl acrylate, and an anhydride. In another further embodiment, the polymeric thickener is polypropylene, polyisoprene, polybutadiene, poly (styrene-butadiene), poly (styrene-ethylene / propylene), poly (ethylene-propylene-diene), polyurethane, polymethacrylate. At least one component selected from the group consisting of lath, polyisobutylene, poly (isobutylene-succinic acid), poly (isobutylene-succinic acid-polyacrylamide), polyurea, polyethylene and combinations thereof.

  In another embodiment, the polymeric thickener comprises a first component and a second component, provided that the first component has a weight average molecular weight greater than the second component. In further embodiments, the weight ratio of the first component to the 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 another further embodiment, the weight ratio of the first component to the second component is between 1: 5 and 1:20, between 1:10 and 1:40, or 1: 5. Between 1:50. In another embodiment, the polymeric thickener does not comprise an ethylene / propylene / norbornadiene copolymer. In a further embodiment, such ethylene / propylene / norbornadiene copolymer does not comprise Nordel IP3745P. In another embodiment, the polymeric thickener does not comprise a styrene / ethylene / propylene copolymer. In further embodiments, such styrene-ethylene / propylene copolymers do not include Septon 1020 or Septon 1001.

  In another embodiment, a method of preparing a suspension composition, wherein (a) a complex comprising a cyclopropene and a molecular encapsulant, an oil medium and a material comprising at least one thickener are placed in a medium mill. And (b) milling the material into a composition comprising solid particles.

  In one embodiment, the suspension composition does not settle for at least 2 weeks, at least 4 weeks, at least 8 weeks, at least 20 weeks or at least 40 weeks. In another embodiment, the oil medium is selected from the group consisting of white mineral oil, hydrotreated intermediate petroleum distillate, hydrotreated light petroleum distillate, and combinations thereof. In a further embodiment, the white mineral oil comprises Blandol and / or Klearol. In another further embodiment, the hydrotreated intermediate petroleum distillate comprises Conosol 260, Unipar SH 260CC, and / or Isopar V. In another further embodiment, the hydrotreated light petroleum distillate comprises Unipar SH 210AS and / or Isopar M.

In one embodiment, the cyclopropene compound is of the formula:

Wherein R is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkylalkyl group, phenyl group or naphthyl group; the substituent is independently halogen, alkoxy Or substituted or unsubstituted phenoxy.

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

In another embodiment, the cyclopropene compound is of the formula:

In the formula, R ¹ is a substituted or unsubstituted C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkenyl group, C ₁ -C ₄ alkynyl group, C ₁ -C ₄ cycloalkyl group, cycloalkylalkyl. A group, a phenyl group or a naphthyl group, and R ² , R ³ and R ⁴ are hydrogen.

  In one embodiment, the cyclopropene comprises 1-methylcyclopropene (1-MCP). In another embodiment, the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, and combinations thereof. In a further embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin.

  In one embodiment, the composition comprises at least 5%, at least 10%, at least 20%, at least 30% by weight of a complex of 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin. At least 40%, at least 50% or at least 60% by weight. In another embodiment, the composition comprises 10% to 20%, 10% to 30%, 10% by weight of a complex of 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin. -40 wt%, 10 wt% to 50 wt%, 10 wt% to 60 wt%, 20 wt% to 40 wt%, 30 wt% to 60 wt%, or 40 wt% to 60 wt%.

  In one embodiment, the composition comprises at least 1 wt%, at least 3 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least one thickener. 30% by weight, at least 40% by weight or at least 50% by weight. In another embodiment, the composition comprises 1% to 20%, 1% to 30%, 1% to 40%, 1% to 50% by weight of the at least one thickener. 5 wt% to 20 wt%, 5 wt% to 40 wt%, 10 wt% to 50 wt%, or 20 wt% to 50 wt%. In another embodiment, the at least one thickener comprises a cellulosic thickener. In another embodiment, the at least one thickener comprises a polymeric thickener. In a further embodiment, the polymeric thickener is formed from at least one of an acrylate, an alkyl acrylate, and an anhydride. In another further embodiment, the polymeric thickener is polypropylene, polyisoprene, polybutadiene, poly (styrene-butadiene), poly (styrene-ethylene / propylene), poly (ethylene-propylene-diene), polyurethane, polymethacrylate. At least one component selected from the group consisting of lath, polyisobutylene, poly (isobutylene-succinic acid), poly (isobutylene-succinic acid-polyacrylamide), polyurea, polyethylene and combinations thereof.

  In another embodiment, the polymeric thickener comprises a first component and a second component, provided that the first component has a weight average molecular weight greater than the second component. In further embodiments, the weight ratio of the first component to the 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 another further embodiment, the weight ratio of the first component to the second component is between 1: 5 and 1:20, between 1:10 and 1:40, or 1: 5. Between 1:50. In another embodiment, the polymeric thickener does not comprise an ethylene / propylene / norbornadiene copolymer. In a further embodiment, such ethylene / propylene / norbornadiene copolymer does not comprise Nordel IP3745P. In another embodiment, the polymeric thickener does not comprise a styrene / ethylene / propylene copolymer. In further embodiments, such styrene-ethylene / propylene copolymers do not include Septon 1020 or Septon 1001.

  When a compound is described herein as being present as a gas in an atmosphere at a certain concentration using the unit “ppm”, the concentration is that compound per million parts by volume of the atmosphere. Is given as a volume part. Similarly, “ppb” means the volume of the compound per billion volume of atmosphere.

The present invention involves the use of one or more cyclopropene compounds. As used herein, a cyclopropene compound is any compound having the formula:

Wherein each R ¹ , R ² , R ³ and R ⁴ is H and a chemical group of the following formula:
-(L) _n -Z
(Where n is an integer from 0 to 12)
Independently selected from the group consisting of Each L is a divalent group. Suitable L groups include, for example, groups containing one or more atoms selected from H, B, C, N, O, P, S, Si or mixtures thereof. The atoms in the L group may be linked to each other by single bonds, double bonds, triple bonds, or mixtures thereof. Each L group may be linear, branched, cyclic, or a combination thereof. In any one R group (ie, any one of R ¹ , R ² , R ^3, and R ⁴ ), the total number of heteroatoms (ie, atoms that are neither H or C) is 0-6 .

  Independently, in any one R group, the total number of atoms other than hydrogen is 50 or less.

  Each Z is a monovalent group. Each Z is hydrogen, halo, cyano, nitro, nitroso, azide, chlorato, bromato, iodoto, isocyanato, isocyanide, isothiocyanato, pentafluorothio and a chemical group G (where G is a 3 to 14 membered ring system) Is independently selected from the group consisting of:

The R ¹ , R ² , R ³ and R ⁴ groups are independently selected from suitable groups. The R ¹ , R ² , R ³ and R ⁴ groups may be the same as each other, or some of them may be different from the others. Groups suitable for use as one or more of R ¹ , R ² , R ³ and R ⁴ include, for example, aliphatic groups, aliphatic-oxy groups, alkylphosphonate groups, alicyclic groups. Groups, cycloalkylsulfonyl groups, cycloalkylamino groups, heterocyclic groups, aryl groups, heteroaryl groups, halogens, silyl groups, other groups, and mixtures and combinations thereof. Groups that are suitable for use as one or more of R ¹ , R ² , R ^3, and R ⁴ may be substituted or unsubstituted. Independently, a group suitable for use as one or more of R ¹ , R ² , R ³ and R ⁴ may be directly linked to the cyclopropene ring, or an intervening group For example, it may be connected to the cyclopropene ring via a hetero atom-containing group.

Suitable R ¹ , R ² , R ³ and R ⁴ groups include, for example, aliphatic groups. Some suitable aliphatic groups include, for example, alkyl groups, alkenyl groups, and alkynyl groups. Suitable aliphatic groups may be linear, branched, cyclic, or combinations thereof. Independently, a suitable aliphatic group can be substituted or unsubstituted.
As used herein, a chemical group of interest is said to be “substituted” if one or more hydrogens of the chemical group of interest are replaced by a substituent. Such substituted groups can be prepared by any method, including but not limited to preparing an unsubstituted form of the chemical group of interest followed by substitution. Is intended. Suitable substituents include, for example, alkyl, alkenyl, acetylamino, alkoxy, alkoxyalkoxy, alkoxycarbonyl, alkoxyimino, carboxy, halo, haloalkoxy, hydroxy, alkylsulfonyl, alkylthio, trialkylsilyl, dialkylamino and their Combinations are included. Further suitable substituents (which, if present, may be present alone or in combination with another suitable substituent) are the following groups:
-(L) _m -Z
Where m is 0 to 8 and L and Z are defined herein above. If more than one substituent is present in only one chemical group of interest, each substituent may replace a different hydrogen atom, or one substituent may be replaced with another substituent. It may be bound to a group (which in turn binds to the chemical group of interest) or a combination thereof.

Suitable R ¹ , R ² , R ³ and R ⁴ groups include, for example, substituted and unsubstituted aliphatic-oxy groups (eg, alkenoxy, alkoxy, alkynoxy and alkoxycarbonyloxy). .

Suitable R ¹ , R ² , R ³ and R ⁴ groups also include, for example, substituted and unsubstituted alkyl phosphonates, substituted and unsubstituted alkyl phosphatos, substituted and non-substituted Substituted alkylamino, substituted and unsubstituted alkylsulfonyl, substituted and unsubstituted alkylcarbonyl, and substituted and unsubstituted alkylaminosulfonyl, including, for example, alkylphosphonate , Dialkyl phosphato, dialkyl thiophosphate, dialkylamino, alkylcarbonyl and dialkylaminosulfonyl.

Suitable R ¹ , R ² , R ³ and R ⁴ groups also include, for example, substituted and unsubstituted cycloalkylsulfonyl and cycloalkylamino groups such as dicycloalkylaminosulfonyl and dicyclo There are alkylamino and the like.

Suitable R ¹ , R ² , R ³ and R ⁴ groups also include, for example, substituted and unsubstituted heterocyclyl groups (ie, aromatic ring groups or non-rings having at least one heteroatom in the ring). Aromatic ring group).

Suitable R ¹ , R ² , R ³ and R ⁴ groups are also substituted and linked to the cyclopropene compound via, for example, an intervening oxy group, amino group, carbonyl group or sulfonyl group There are unsubstituted heterocyclyl groups; examples of such R ¹ , R ² , R ³ and R ⁴ groups include heterocyclyloxy, heterocyclylcarbonyl, diheterocyclylamino and diheterocyclylaminosulfonyl.

Suitable R ¹ , R ² , R ³ and R ⁴ groups also include, for example, substituted and unsubstituted aryl groups. Suitable substituents are those described herein above. In some embodiments, one or more substituted aryl groups are used, where at least one substituent is alkenyl, alkyl, alkynyl, acetylamino, alkoxyalkoxy, alkoxy, alkoxycarbonyl, carbonyl, One or more of alkylcarbonyloxy, carboxy, arylamino, haloalkoxy, halo, hydroxy, trialkylsilyl, dialkylamino, alkylsulfonyl, sulfonylalkyl, alkylthio, thioalkyl, arylaminosulfonyl and haloalkylthio.

Suitable R ¹ , R ² , R ³ and R ⁴ groups also include, for example, a cyclopropene compound via an intervening oxy group, amino group, carbonyl group, sulfonyl group, thioalkyl group or aminosulfonyl group. There are substituted and unsubstituted heterocyclic groups linked; examples of such R ¹ , R ² , R ³ and R ⁴ groups include diheteroarylamino, heteroarylthioalkyl and di And heteroarylaminosulfonyl.

Suitable R ¹ , R ² , R ³ and R ⁴ groups also include, for example, hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, nitroso, azide, chlorato, bromato, iodato, isocyanato, isocyanide , Isothiocyanato, pentafluorothio; acetoxy, carboethoxy, cyanato, nitrato, nitrito, perchlorato, allenyl; butyl mercapto, diethylphosphonate, dimethylphenylsilyl, isoquinolyl, mercapto, naphthyl, phenoxy, phenyl, piperidino, pyridyl, quinolyl, triethyl Silyl, trimethylsilyl; and their substituted analogs.

  As used herein, the chemical group G is a 3 to 14 membered ring system. Ring systems suitable as chemical group G may be substituted or unsubstituted; such ring systems may be aromatic (including, for example, phenyl and naphthyl) or aliphatic (unsaturated Aliphatic, partially saturated aliphatic or saturated aliphatic); such ring systems may be carbocyclic or heterocyclic. Among the heterocyclic G groups, some suitable heteroatoms are, for example, nitrogen, sulfur, oxygen and combinations thereof. Suitable ring systems for chemical group G may be monocyclic, bicyclic, tricyclic, polycyclic, spiro or condensed; bicyclic, tricyclic or condensed Among suitable chemical group G ring systems, the various rings in one chemical group G may all be of the same type, or may be of more than one type (eg, aromatic The ring may be condensed with an aliphatic ring).

  In some embodiments, G is a ring system containing a saturated or unsaturated 3-membered ring (such as a saturated or unsaturated cyclopropane ring, cyclopropene ring, epoxide ring, or aziridine ring).

  In some embodiments, G is a ring system that contains a 4-membered heterocyclic ring; in some of such embodiments, the heterocyclic ring contains exactly one heteroatom. Independently, in some embodiments, G is a ring system containing 5 or more heterocyclic rings; in some of such embodiments, 1 to 4 heterocyclic rings Containing heteroatoms. Independently, in some embodiments, the ring in G is unsubstituted; in other embodiments, the ring system contains 1-5 substituents; in those embodiments where G contains a substituent. In some, each substituent is independently selected from the substituents described hereinabove. Also suitable are embodiments in which G is a carbocyclic ring system.

  In some embodiments, each G is independently substituted or unsubstituted phenyl, pyridyl, cyclohexyl, cyclopentyl, cycloheptyl, pyrrolyl, furyl, thiophenyl, triazolyl, pyrazolyl, 1,3-dioxolanyl, or morpholinyl. It is. Among these embodiments, for example, include those embodiments in which G is unsubstituted or substituted phenyl, cyclopentyl, cycloheptyl, or cyclohexyl. In some of these embodiments, G is cyclopentyl, cycloheptyl, cyclohexyl, phenyl, or substituted (substituted) phenyl. In embodiments where G is substituted phenyl, for example, there may be one, two or three substituents present. Independently, embodiments in which G is substituted phenyl also include those embodiments in which the substituent is independently selected from methyl, methoxy and halo.

Also contemplated are embodiments in which R ³ and R ⁴ are taken together to form a group that is attached to the carbon atom at the 3-position of the cyclopropene ring by a double bond. Some such compounds are described in US Patent Application Publication No. 2005/0288189.

In some embodiments, one or more cyclopropene compounds are used in which one or more of R ¹ , R ² , R ^3, and R ⁴ is hydrogen. In some embodiments, R ¹ or R ² or both R ¹ and R ² are hydrogen. Independently, in some embodiments, R ³ or R ⁴ or both R ³ and R ⁴ are hydrogen. In some embodiments, R ² , R ^3, and R ⁴ are hydrogen.

In some embodiments, one or more of R ¹ , R ² , R ^3, and R ⁴ is a structure that has no double bonds. Independently, in some embodiments, one or more of R ¹ , R ² , R ^3, and R ⁴ is a structure that has no triple bonds. Independently, in some embodiments, one or more of R ¹ , R ² , R ^3, and R ⁴ is a structure that has no halogen atom substituents. Independently, in some embodiments, one or more of R ¹ , R ² , R ^3, and R ⁴ is a structure that has no substituent that is ionic.

In some embodiments, one or more of R ¹ , R ² , R ^3, and R ⁴ is hydrogen or (C ₁ -C ₁₀ ) alkyl. In some embodiments, each of R ¹ , R ² , R ^3, and R ⁴ is hydrogen or (C ₁ -C ₈ ) alkyl. In some embodiments, each of R ¹ , R ² , R ^3, and R ⁴ is hydrogen or (C ₁ -C ₄ ) alkyl. In some embodiments, each of R ¹ , R ² , R ^3, and R ⁴ is hydrogen or methyl. In some embodiments, R ¹ is (C ₁ -C ₄ ) alkyl and each of R ² , R ^3, and R ⁴ is hydrogen. In some embodiments, R ¹ is methyl and each of R ² , R ^3, and R ⁴ is hydrogen, and the cyclopropene compound is defined herein as 1-methylcyclopropene or “1-MCP”. It is known in the book.

  In some embodiments, a cyclopropene compound is used that has a boiling point at 1 atm of 50 ° C. or lower, or 25 ° C. or lower, or 15 ° C. or lower. Independently, in some embodiments, a cyclopropene compound having a boiling point at 1 atm of −100 ° C. or higher, −50 ° C. or higher, or −25 ° C. or higher, or 0 ° C. or higher is used. Is done.

  The cyclopropene compound applicable to the present invention may be prepared by any method. Some suitable methods for preparing cyclopropene compounds are the processes disclosed in US Pat. Nos. 5,518,988 and 6,017,849.

  The composition of the present invention may comprise at least one molecular encapsulating agent. In some embodiments, at least one molecular encapsulating agent encapsulates one or more cyclopropene compounds or a portion of one or more cyclopropene compounds. A complex containing a cyclopropene compound molecule or a portion of a cyclopropene compound molecule encapsulated in a molecule encapsulating agent molecule is known herein as a “cyclopropene complex”.

  In some embodiments, there is at least one cyclopropene complex that is an inclusion complex. In such inclusion complexes, the molecular encapsulating agent forms a cavity and the cyclopropene compound or a portion of the cyclopropene compound is located inside the cavity. In some such inclusion complexes, there is no covalent bond between the cyclopropene compound and the molecular encapsulating agent. Independently, in some of such inclusion complexes, the electrostatic attraction is whatever the electrostatic attraction is one or more polar components in the cyclopropene compound and one or more in the molecular encapsulating agent. Regardless of whether or not it exists between the above polar components, there is no ionic bond between the cyclopropene compound and the molecule-encapsulating complex.

  Independently, in some such inclusion complexes, the interior of the molecular encapsulant cavity is substantially non-polar or hydrophobic or both, and the cyclopropene compound (or cyclohexane located within the cavity) Some of the propene compounds are also substantially apolar or hydrophobic or both. While the present invention is not limited to any particular theory or mechanism, in such a non-polar cyclopropene complex, van der Waals forces or hydrophobic interactions or both are encapsulated in the cyclopropene compound molecule or a portion thereof. It is intended to cause staying in the agent cavity.

  The complex of the cyclopropene compound and the molecular encapsulating agent may be prepared by any means. In one method of preparation, for example, such a complex contacts a cyclopropene compound with a solution or slurry of a molecular encapsulant, after which the complex is disclosed, for example, in US Pat. No. 6,017,849. It is prepared by isolation using a process. For example, in one method of preparing a complex in which cyclopropene is encapsulated in a molecular encapsulant, cyclopropene gas is blown into a solution of molecular encapsulant in water, from which the complex first precipitates. And then isolated by filtration. In some embodiments, the complex is prepared by the method described above, and after isolation, is dried and stored in solid form, eg, as a powder, for subsequent addition to useful compositions.

  The amount of molecular encapsulating agent can be usefully characterized by the ratio of moles of molecular encapsulating agent to moles of cyclopropene. In some embodiments, the ratio of moles of molecular encapsulating agent to moles of cyclopropene may be 0.1 or more, 0.2 or more, 0.5 or more, or 0.9 or more. Independently, in some such embodiments, the ratio of moles of molecular encapsulating agent to moles of cyclopropene may be 2 or less or 1.5 or less.

  Suitable molecular encapsulating agents include, for example, organic and inorganic molecular encapsulating agents. Suitable organic molecular encapsulating agents include, for example, substituted cyclodextrins, unsubstituted cyclodextrins, and crown ethers. Suitable inorganic molecular encapsulating agents include, for example, zeolites. Also suitable are mixtures of suitable molecular encapsulating agents. In some embodiments, the encapsulating agent is alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin or a mixture thereof. In some embodiments of the invention, alpha-cyclodextrin is used. Preferred molecular encapsulating agents will vary depending on the structure of the cyclopropene compound being used. Any cyclodextrin or mixture of cyclodextrins, cyclodextrin polymer, modified cyclodextrins or mixtures thereof can also be utilized in accordance with the present invention. Some cyclodextrins are available, for example, from Wacker Biochem Inc. (Adrian, MI) or Cerestar USA (Hammond, IN), as well as from other suppliers.

  In the practice of the present invention, one or more oils are used. As used herein, an “oil” is a compound that is liquid at 25 ° C. and 1 atmosphere and has a boiling point of 30 ° C. or more at 1 atmosphere. As used herein, “oil” does not contain water, does not contain surfactant (as described herein), and (as described herein). N) Does not contain dispersant.

  In some embodiments, one or more oils having a boiling point of 50 ° C. or higher, or 75 ° C. or higher, or 100 ° C. or higher may be used. In some embodiments, any oil used has a boiling point of 50 ° C. or higher. In some embodiments, any oil used has a boiling point of 75 ° C or higher. In some embodiments, any oil used has a boiling point of 100 ° C or higher. Independently, in some of the embodiments using oil, one or more oils having an average molecular weight of 100 or higher, or 200 or higher, or 500 or higher may be used. In some embodiments, any oil used has an average molecular weight of 100 or greater. In some embodiments, any oil used has an average molecular weight of 200 or greater. In some embodiments, any oil used has an average molecular weight of 500 or greater.

  The oil is a hydrocarbon oil (ie, an oil whose molecule contains only carbon and hydrogen atoms) or a non-hydrocarbon oil (ie, the molecule contains at least one atom that is neither carbon nor hydrogen) Oil).

  Some suitable hydrocarbon oils include, for example, linear alkane compounds, branched alkane compounds, or cyclic alkane compounds having 6 or more carbon atoms. Some other suitable hydrocarbon oils are, for example, one or more carbon-carbon double bonds, one or more carbon-carbon triple bonds, or one or more fragrances. The group rings are optionally in combination with each other and / or in combination with one or more alkane groups. Some suitable hydrocarbon oils are obtained from petroleum distillation and contain a mixture of various compounds, optionally with impurities. Hydrocarbon oils obtained from petroleum distillation may contain a relatively broad mixture of various compositions or may contain a relatively pure composition. In some embodiments, hydrocarbon oils containing 6 or more carbon atoms are used. In some embodiments, hydrocarbon oils containing 18 or fewer carbon atoms are used. In some embodiments, any hydrocarbon oil used contains 18 or fewer carbon atoms. In some embodiments, any hydrocarbon oil used contains 6 or more carbon atoms. Some suitable hydrocarbon oils include, for example, hexane, decane, dodecane, hexadecane, diesel oil, hydrotreated light petroleum distillate, hydrotreated intermediate petroleum distillate, refined paraffinic oil (e.g. , Ultrafine ™ spray oil from Sun Company), and mixtures thereof. In some embodiments, any hydrocarbon oil used is a hydrocarbon oil.

  Among embodiments that use non-hydrocarbon oils, some suitable non-hydrocarbon oils are, for example, fatty non-hydrocarbon oils. “Fatty” means herein any compound containing one or more residues of fatty acids. Fatty acids are long-chain carboxylic acids and have a chain length of at least 4 carbon atoms. Typical fatty acids have a chain length of 4-18 carbon atoms, but some have longer chains. Linear, branched or cyclic aliphatic groups may be attached to this long chain. Fatty acid residues may be saturated or unsaturated and may contain functional groups that are either naturally occurring or attached, such as, for example, An alkyl group, an epoxide group, a halogen, a sulfonate group or a hydroxyl group. Some suitable fatty non-hydrocarbon oils include, for example, fatty acids, esters of fatty acids, amides of fatty acids, their dimers, trimers, oligomers or polymers, and mixtures thereof.

  Some of the suitable fatty non-hydrocarbon oils are, for example, esters of fatty acids. Such esters include, for example, fatty acid glycerides. Glycerides are esters of fatty acids with glycerol and may be monoglycerides, diglycerides or triglycerides. A variety of triglycerides are found in nature. Most naturally occurring triglycerides contain residues of fatty acids of several different lengths and / or compositions. Some suitable triglycerides are found in animal sources such as dairy products, animal fats or fish. Further examples of suitable triglycerides are oils found in plants such as palm oil, palm oil, cottonseed oil, olive oil, tall oil, peanut oil, safflower oil, sunflower oil, corn oil, soybean oil, linseed oil, giraffe Examples thereof include oil, castor oil, canola oil, citrus seed oil, cacao oil, oat oil, palm oil, palm kernel oil, rice bran oil, quarife oil or rapeseed oil.

  Regardless of where it is found, suitable triglycerides include, for example, triglycerides containing at least one fatty acid residue having 14 or more carbon atoms. Some suitable triglycerides leave fatty acid residues having 14 or more carbon atoms, fatty acid residues having 16 or more carbon atoms, or fatty acid residues having 18 or more carbon atoms It has a fatty acid residue containing 50% by weight or more based on the weight of. An example of a suitable triglyceride is soybean oil.

  Suitable fatty non-hydrocarbon oils may be synthetic or natural or may be modified natural oils or combinations or mixtures thereof. Good. Suitable modifications of natural oils include, for example, alkylation, hydrogenation, hydroxylation, alkyl hydroxylation, alcoholysis, hydrolysis, epoxidation, halogenation, sulfonation, oxidation, polymerization and combinations thereof. In some embodiments, alkylated oils (eg, including methylated oils and ethylated oils) are used. One suitable modified natural oil is methylated soybean oil.

Suitable fatty non-hydrocarbon oils also include self-emulsifying esters of fatty acids.
Another group of suitable non-hydrocarbon oils is a group of silicone oils. Silicone oil is an oligomer or polymer having a skeleton partially or wholly composed of —Si—O— bonds. Silicone oil includes, for example, polydimethylsiloxane oil. Polydimethylsiloxane oil is an oligomer or polymer containing units of the following form:

Wherein at least one of the units, with a X1 = CH _3. In other units, X1 can be any other group capable of bonding to Si, including, for example, hydrogen, hydroxyl, alkyl, alkoxy, hydroxyalkyl, hydroxyalkoxy, alkylpolyalkoxyl. , Their substituted forms, or combinations thereof. Substituents may include, for example, hydroxyl, alkoxyl, polyethoxyl, ether bond, ester bond, amide bond, other substituents, or any combination thereof. In some embodiments, any oil used is silicone oil.

  In some suitable polydimethylsiloxane oils, all X1 groups are non-hydrophilic groups. In some suitable polydimethylsiloxane oils, all X1 groups are alkyl groups. In some suitable polydimethylsiloxane oils, all X1 groups are methyl. In some embodiments, every silicone oil is a polydimethylsiloxane oil in which the X1 group is methyl. In some suitable polydimethylsiloxanes, at least one unit has a non-methyl X1 group; if two or more non-methyl X1 units are present, such non-methyl X1 units are the same as each other. There may be two or more X1 units other than different methyl. Polydimethylsiloxane oils may be endcapped with any of a wide variety of chemical groups including, for example, hydrogen, methyl, other alkyls, or combinations thereof. Cyclic polydimethylsiloxane oil is also contemplated. Suitable oil mixtures are also suitable.

  The practice of the present invention involves particles suspended in an oil medium. The oil medium can be any of the oils described hereinabove. By “suspended” herein, the particles are insoluble or only slightly soluble in oil, and the particles form an oil (this forms a continuous medium around the particles). ) Is distributed throughout. A system of particles suspended in oil is known herein as a “suspension”. The suspension of the present invention is stable. That is, under standard conditions of 25 ° C., 1 atmosphere and standard gravity, most of the particles (at least 80 wt% based on the total dry weight of the particles) do not settle to the bottom of the container when stored for 1 day. Will not float on top of the container. In some embodiments, the amount of particles that settle to the bottom of the container upon storage is 10% or less, or 5% or less, or 2% or less, by weight based on the total dry weight of the particles. Or 1% or less. Independently, in some embodiments, a suspension is used that is stable when stored for more than 2 days, or more than 5 days, or more than 10 days.

  The collection of particles can be evaluated to determine its size. One suitable evaluation method is, for example, inspection using a microscope. An image of the particles, for example such an image obtained with a microscope, may be visually inspected and evaluated, possibly with reference to a length standard, or alternatively, the image may be an appropriate image It may be examined and evaluated by analytical methods (eg, computer programs).

  In embodiments where the particles are not spherical, it is useful to characterize the particles by the maximum size of each particle. A collection of particles may be characterized by the largest median value. That is, half of the particles (weight ratio) in a cluster will have a maximum size that is greater than the median value of the cluster. In the practice of the present invention, when the collection of particles suspended in the oil medium is evaluated, the median value is 50 micrometers or less. In some embodiments, particles are used whose median value is 20 micrometers or less, or 10 micrometers or less, or 5 micrometers or less, or 2 micrometers or less.

  A non-dependent measure of particles is the aspect ratio, which is the ratio of the maximum particle size to the minimum particle size. The aspect ratio is independent of particle size. In some embodiments of the invention, the collection of particles suspended in the oil medium has an aspect ratio of 20 or less, or 10 or less, or 5 or less, or 2 or less.

  The particles suspended in the oil medium are solid. That is, some or all of the particles are manufactured from a material that is in a solid state. Each particle may be porous or non-porous, or may or may not have one or more voids, or one or It may or may not have more cavities, and each pore or void or cavity (if present) is partly or wholly depending on the material that is a solid, liquid or gas May or may not be occupied. A system of particles suspended in an oil medium is synonymously known as a “dispersion”.

  The particles suspended in the oil medium may contain cyclopropene and molecular encapsulating agent. In some embodiments, some or all of the cyclopropene present in the composition is part of a cyclopropene complex. Although the present invention is not limited to any particular theory or model, it is intended that most or all of the cyclopropene molecules present in the composition exist in the form of molecules that are part of the cyclopropene complex. Any cyclopropene molecule in the composition that is not part of the cyclopropene complex can be adsorbed, for example, in solution or at the interface, somewhere else, or a combination thereof. It is further intended to exist in In some embodiments, the amount of cyclopropene present as part of the cyclopropene complex may be 80% or more, or 90% or more, by weight based on the total amount of cyclopropene in the composition. May be 95% or more, or may be 99% or more.

  In some embodiments of the invention, the oil medium includes one or more dispersants. Part or all of the dispersion is dissolved in the oil, part or all of the dispersion is located on the particle surface (ie, at the boundary between the particle and the oil medium), or a combination thereof Is intended. In addition, a small amount of dispersant is located in one or more other places, for example on the surface of the oil, on the wall of the container, in complex with the molecular encapsulant, or combinations thereof. Is intended (or the dispersant may not be located at such location).

  As defined herein, a “dispersant” is a compound that can help solid particles form a stable suspension in a liquid medium. Most dispersants work by minimizing that the particles can essentially agglomerate with larger particles that are more likely to settle (or cream). In some embodiments, suitable dispersants have one or more hydrophilic groups. Independently, in some embodiments, suitable dispersants have a large number of hydrophobic groups. Some suitable hydrophobic groups include, for example, organic groups having 8 or more consecutive carbon atoms. In some embodiments, there are hydrophobic groups having 10 or more consecutive carbon atoms. Regardless of the number of carbon atoms, such organic groups may be linear, cyclic, branched, or combinations thereof. Independently, such an organic group may be a hydrocarbon or may be substituted. Independently, such organic groups can be saturated or unsaturated.

  Some suitable dispersants have two or more hydrophobic groups per molecule, or three or more hydrophobic groups, or four or more hydrophobic groups, or five or more Has a hydrophobic group. In some embodiments, every dispersant has 4 or more hydrophobic groups per molecule. In some embodiments, every dispersant has 5 or more hydrophobic groups per molecule.

  Regardless of the nature of the hydrophobic group, some suitable dispersants have one or more hydrophilic groups. Some suitable hydrophilic groups include, for example, groups that can be ionized in water over a certain range of pH, including, for example, carboxyl groups, sulfate groups, sulfonate groups, and amide groups. Other suitable hydrophilic groups are nonionic. Some suitable nonionic hydrophilic groups include, for example, segments of a polymer that would be soluble in water if present independently as a polymer. Such hydrophilic segments of the polymer include, for example, polyethylene glycol segments.

  In embodiments where a dispersant is used in which the molecule contains both a hydrophobic group and at least one hydrophilic group, these groups may be attached to the dispersant molecule in any manner. For example, some suitable dispersants are block copolymers with at least one block that is a segment of polyethylene glycol and at least one block that contains a plurality of hydrophobic groups. An example of a block containing a plurality of hydrophobic groups is a segment of poly (12-hydroxystearic acid). Another example of a block containing a plurality of hydrophobic groups is an alkyd polymer segment. Alkyd polymers are copolymers of polyols, polybasic acids and fatty acids or triglyceride oils.

As used herein, a nonionic dispersant is a dispersant in which all of the hydrophilic groups are nonionic. In some embodiments, at least one nonionic dispersant is used. In some embodiments, any dispersant used is nonionic.
One useful property of a nonionic dispersant is the HLB value, which is defined by the following formula:
HLB = 20 ^* M _H / M
Where _MH is the molecular weight of the hydrophilic portion of the molecule and M is the molecular weight of the molecule.

  Regardless of whether they are ionic or nonionic, the molecule of interest may be characterized by an acid number (which is synonymously referred to as an “acid value”). The acid number is the number of milligrams of KOH required to neutralize the target molecule per gram of target molecule. One method for testing acid number is shown in ASTM D-7253. It will be appreciated that some details of this test (eg, solvent and / or indicator selection, etc.) can be tailored as needed for the particular molecule of interest.

  In some embodiments where one or more non-ionic dispersants are used, one or more of these dispersants has an HLB greater than 4, or an HLB greater than 5. Have Independently, in some embodiments, one or more dispersants having an HLB of less than 8 or an HLB of 7 or less are used. In some embodiments, any dispersant used has an HLB that is 5-7.

  In some embodiments where one or more nonionic dispersants are used without depending on the HLB value of the dispersant, one or more of these dispersants may be in mg KOH / The acid value in units of g is 10 or less, or 9 or less, or 8 or less. Independently, in some embodiments where one or more nonionic dispersants are used, one or more of these dispersants has an acid number in units of mg KOH / g. Is 2 or more, 4 or more, or 6 or more. In some embodiments, any dispersant used has an acid number that is 6 mg KOH / g to 8 mg KOH / g.

  In some embodiments, one or more dispersants having an acid number of 6 mg KOH / g to 8 mg KOH / g or higher are used, provided that this same dispersant is also 5 to HLB is 7.

  In some embodiments, one or more surfactants are used. “Surfactant”, as used herein, is synonymous with “emulsifier” and means a compound that aids in the formation of a stable suspension of oil droplets in water. The molecule of the surfactant compound contains at least one hydrophilic group and at least one hydrophobic group. Surfactants are usually classified according to the nature of the hydrophilic group. Suitable surfactants include, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and mixtures thereof.

  In embodiments where one or more anionic surfactants are used, some suitable anionic surfactants include, for example, sulfosuccinates (eg, monoalkylsulfosuccinates and dialkylsulfates). Succinate alkali salts), sulfates and sulfonates (eg including alkyl sulfate alkali salts). In some embodiments, no anionic surfactant is used.

  Among embodiments in which one or more cationic surfactants are used, some suitable cationic surfactants include, for example, amine-based surfactants and quaternary ammonium salt type surfactants. Agent is included. In some embodiments, no cationic surfactant is used.

  In some embodiments, one or more nonionic surfactants are used. Among embodiments in which one or more nonionic surfactants are used, some suitable nonionic surfactants include, for example, fatty ethoxylates, fatty acid esters of polyhydroxy compounds, amides Oxides, alkyl oxide block copolymers, silicone-based nonionic surfactants, fluorosurfactants and mixtures thereof are included.

  Suitable fatty ethoxylates include, for example, fatty alcohol ethoxylates, fatty acid ethoxylates, fatty ethanolamide ethoxylates, and fatty amine ethoxylates. Suitable ethoxy of fatty alcohols include, for example, fatty alcohol ethoxylates having any combination of the following characteristics: linear or branched; primary or secondary; alkyl or alkyl Aryl. In some embodiments, one or more fatty ethoxylates are used that are arylalkyl ethoxylates, fatty alcohol ethoxylates, or mixtures thereof.

Suitable silicone nonionic surfactants include, for example, silicone nonionic surfactants having the formula:

Where n is 1 to 5, m is 0 to 4 and Q is:

In the formula, p is 1 to 6, and q is 3 to 20. In some embodiments, n is 1. Independently, in some embodiments, m is zero. Independently, in some embodiments, p is 3. Independently, in some embodiments, q is 7 or 8 or a mixture thereof. One further example of a suitable nonionic surfactant is Atplus595. Also suitable are mixtures of suitable surfactants.

  Nonionic surfactants may usefully be characterized by HLB (as defined herein above). In some embodiments, one or more nonionic surfactants with an HLB of 3-4 are used. Independently, in some embodiments, one or more nonionic surfactants with an HLB of 8-10 are used. In some embodiments, one or more nonionic surfactants having an HLB of 3-4, as well as one or more nonionic surfactants having an HLB of 8-10 A mixture of surfactants is used.

  In some embodiments (these are referred to herein as “continuous oil” embodiments), the continuous medium of the composition of the invention is an oil medium in which the particles are suspended. In some continuous oil embodiments, one or more surfactants are present in the composition. In some continuous oil embodiments, no surfactant is present in the composition. Independently, in some continuous oil embodiments, little or no water is present; that is, in such embodiments, if some water is present, the amount of water is the composition 5% or less, or 2% or less, or 1% or less, or 0.5% or less, or 0.1% or less.

  In some continuous oil embodiments, the amount of cyclopropene is 1 gram of cyclopropene (“g / L”) or more per liter of oil, or 2 g / L or more, or 5 g / L. Or more, or 10 g / L or more, or 20 g / L or more. Independently, in some continuous oil embodiments, the amount of cyclopropene is 200 g / L or less, or 100 g / L or less, or 50 g / L or less.

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

  In some continuous oil embodiments, the amount of surfactant is 0.5% or more, or 1% or more, or 2% or more, by weight based on the weight of the composition. Independently, in some continuous oil embodiments, the amount of surfactant is 20% or less, or 10% or less, by weight based on the weight of the composition. In some continuous oil embodiments, no surfactant is present.

  In some continuous water embodiments, one or more surfactants are present in the composition. In some continuous water embodiments, one or more nonionic surfactants are present in the composition. In some continuous water embodiments, one or more nonionic surfactants with an HLB of 3-4 are present in the composition and one or more with an HLB of 8-10 Nonionic surfactants are also present in the composition. In some embodiments, selection of one or more surfactants is performed. This is because such surfactants are well suited for emulsifying specific oil media droplets that are used as oil media in that embodiment.

  In some continuous water embodiments, the amount of cyclopropene, by weight based on the weight of the composition, is 10 parts per million (ppm) or more, or 20 ppm or more, or 50 ppm or more. Independently, in some continuous water embodiments, the amount of cyclopropene, by weight based on the weight of the composition, is 500 ppm or less, or 200 ppm or less.

  In some continuous water embodiments, the amount of dispersant, by weight based on the weight of the composition, is 2.5 ppm or more, or 10 ppm or more, or 50 ppm or more, or 200 ppm or more. Independently, in some continuous water embodiments, the amount of dispersant is 1250 ppm or less, or 1000 ppm or less, or 750 ppm or less, by weight based on the weight of the composition.

  In some continuous water embodiments, the amount of surfactant in a weight ratio based on the weight of the composition is 0.02% or more in a weight ratio of dry surfactant based on the weight of the composition; Alternatively, it is 0.05% or more, or 0.1% or more, or 0.2% or more. Independently, in some continuous water embodiments, the amount of surfactant by weight based on the weight of the composition is 2% or less by weight of dry surfactant based on the weight of the composition. Yes, or 1% or less, or 0.5% or less.

  The composition of the present invention may be produced by any method. In some suitable methods, the starting materials are oils, dispersants, optionally used surfactants, and cyclopropene complexes. In some embodiments, the starting material cyclopropene complex is in the form of powder particles containing the cyclopropene complex, and the powder particles are 50 micrometers when the median size is measured by the maximum size. Much larger (eg, 200 micrometers or more). In some embodiments, the starting material may be placed in a media mill and then milled until the desired particle size is obtained. In some embodiments, this milling process is performed when the particles are measured by maximum size, 50 micrometers or less, or 20 micrometers or less, or 10 micrometers or less, or 5 micrometers or less, or 2 This is done until it has a median size of micrometer or less.

  In some embodiments involving milling, the mixture to be milled is cyclopropene complex powder in an amount of 2% or more by weight based on the weight of the mixture to be milled, or an amount of 5% or more. Or in an amount of 10% or more, or in an amount of 20% or more. Independently, in some embodiments involving milling, the milled mixture comprises cyclopropene complex powder in an amount of 60% or less by weight based on the weight of the milled mixture, or 50 It contains in the quantity below%.

  In some embodiments involving milling, the milled mixture comprises a dispersant in an amount of 0.02% or more by weight based on the weight of the mixture to be milled, or 0.05% or more. It is contained in an amount, 0.1% or more, 0.2% or more, 0.5% or more, or 1% or more. Independently, in some embodiments involving milling, the mixture to be milled comprises dispersing agent in an amount of 10% or less by weight based on the weight of the mixture to be milled, or 7% or less. Contained in an amount or 5% or less.

  In some embodiments involving milling, the mixture to be milled comprises a surfactant in an amount of 0.2% or more by weight based on the weight of the mixture to be milled, or 0.5% or more. In an amount of 1% or more. Independently, in some embodiments involving milling, the mixture to be milled comprises a surfactant in an amount of 30% or less by weight based on the weight of the mixture to be milled, or 10% or less. Or in an amount of 6% or less. In some embodiments involving milling, the mixture to be milled does not contain any surfactant.

  In some embodiments involving milling, the mixture to be milled contains oil in an amount of 40% or more, or 50% or more by weight based on the weight of the mixture to be milled. Independently, in some embodiments involving milling, the mixture to be milled is oil in an amount of 98% or less, or an amount of 80% or less, by weight based on the weight of the mixture to be milled. Or in an amount of 70% or less.

  In some embodiments involving milling, water is removed from the starting material, from the mixture to be milled, and from the milled mixture when stored. That is, in such embodiments, the amount of water in the mixture of starting materials is 2% or less, or 1% or less, or 0.5% or less by weight ratio based on the total weight of the starting materials. Or 0.2% or less, or 0.1% or less, or zero. In such embodiments, the same amount of water is intended for the mixture during the milling period and for the milled mixture when stored. The mixture during storage may or may not have a greater amount of water than the mixture during milling. Independently, the mixture during the milling period may or may not have a greater amount of water than the mixture of starting materials prior to milling.

  The product of such a milling process may be used immediately or stored.

  When it is desired to implement a continuous oil embodiment, the product of the milling process may be used as is, or additional oil may be added to the product of such a milling process. .

  When it is desired to implement a continuous water embodiment, the product of such a milling process will be broken into droplets and suspended in an aqueous medium. In some embodiments, the milling process product may be added to an aqueous medium and subjected to agitation, and the milling process product will be divided into suspended droplets. In some such embodiments, one or more surfactants are selected to help the product of the milling process be separated and suspended in an aqueous medium, such one Or more surfactant is added to the starting material and included in the mixture to be milled. Whether one or more surfactants are added to the product of the milling process after the milling process is complete, whether or not the surfactant is included in the mixture to be milled Alternatively, it may be added to the aqueous medium (before or after the aqueous medium is mixed with the product of the milling process).

  In general, whenever a cyclopropene complex is used, direct contact of the cyclopropene complex with water sometimes results in the release of cyclopropene from the complex faster than desired, and It is known that cyclopropene can be lost (eg, via diffusion from the composition, via chemical reactions, or combinations thereof). In the practice of the continuous water embodiment of the present invention, the cyclopropene complex remains in the oil medium so that contact between the cyclopropene complex and water is minimized or eliminated, and thus the composition It is intended that a desirable percentage of the cyclopropene molecule remains in the composition.

  One possible use for the composition of the invention is to treat the plant or plant part by contacting the composition of the invention with the plant or plant part. Plants that provide useful plant parts are known herein as “crop plants”. The treatment may be performed on growing plants or on plant parts harvested from growing plants. When treatment is performed on a growing plant, it is intended that the composition of the present invention may be contacted with the whole plant or may be contacted with one or more plant parts. Is done. Plant parts can be any part of a plant, including, for example, flowers, buds, (decorative) flowers, seeds, branches, roots, bulbs, fruits, edible parts, leaves and combinations thereof. included.

  The removal of useful plant parts from crop plants is known as harvesting. In some embodiments, crop plants are treated with the compositions of the present invention prior to harvesting useful plant parts.

  The composition of the present invention may be contacted with a plant or plant part by any method including, for example, spraying, dipping, drenching, fogging and combinations thereof. is there. In some embodiments, spraying is used.

  Suitable treatments may be performed on fields, vegetable gardens / orchards, buildings (eg, greenhouses), or plants that are planted elsewhere. Suitable treatments are for open land, one or more containers (eg, pots, planters or vases, etc.), limited or raised nurseries, or plants planted elsewhere It may be done. In some embodiments, the treatment is performed on plants that are in a non-building location. In some embodiments, plants are treated while growing in containers (eg, pots, flat boxes or transportable nurseries).

  Many of the plants that are suitable for use in the practice of the present invention can be usefully divided into several categories or groups. One useful method for defining such groups is the “Definition and Classification of” published as a “draft” by the United Nations Food and Agriculture Organization (“FAO”) on or before March 23, 2006. Commodities ".

  In the practice of some embodiments of the present invention, it is contemplated to use plants that result in one or more crops included in any one of the following crop groups.

  The first group of crops is cereals, for example, wheat, rice, barley, corn, popcorn, rye, oats, millet, sorghum, buckwheat, kiona, fonia, triticale, canary seeds. , Canagua, quihuicha, adlay, makomo and other cereals. In some embodiments of the invention, suitable plants are those that yield wheat or rice or corn or sorghum. In some embodiments, corn plants are preferred. In some embodiments, wheat plants are preferred. The second group of plants are roots and tubers.

  A third group of plants are sugar crops, including, for example, sugar cane, sugar beet, sugar maple, sugar maize, sugar palm and other sugar crops. The fourth group of plants is beans, which include, for example, kidney beans, chickpeas, garbanzo, cowpeas, pigeons, lentils and other beans. The fifth group of plants are nuts, including, for example, Brazil nuts, cashew nuts, chestnuts, almonds, walnuts, pistachios, hazelnuts, pecan nuts, macadamia nuts and other nuts.

  Group 6 crops are oil-impregnated crops, for example, soybean, American potato (including peanuts), coconut, oil palm, olive, shea butter, sunflower seed, sunflower seed, rapeseed, canola , Brachid seeds, safflower seeds, sesame seeds, mustard seeds, poppy seeds, melon seeds, peanut seeds, kapok seeds, cotton seeds, flaxseed, hemp seeds and other oil seeds included. In some embodiments, soybean plants are preferred.

  Group 7 crops are vegetables such as cabbage, artichoke, asparagus, lettuce, spinach, cassava leaves, tomatoes, cauliflower, pumpkins, cucumbers and gherkins, eggplant, chili and pepper, green onions, Dry onion, garlic, leek, other green onion vegetables, green beans, green peas, green broad bean, green beans, carrots, okra, blue corn, mushrooms, watermelon, cantaloupe melon (Cantaloupe melon), bamboo shoot, beet, chard, caper, cardon, celery, chervil, cress, fennel, horseradish, majorana, barramundin, parsley, American gulp, radish Rhubarb, rutabaga, savory, scorzonera, sorrel, include watercress, and other vegetables.

  Group 8 crops are fruits, which include, for example, bananas and culinary bananas; citrus fruits; pear fruits; stone fruits; berries; grapes; tropical fruits; included. The ninth group of plants are fibers, including, for example, cotton, flax, Asa, Kapok, jute, ramie, sisal as well as other fibers from plants. In some embodiments, cotton plants are preferred. The tenth group of plants is a spice. Group 11 plants are feed crops. Forage crops are crops that are mainly grown for animal feed. Group 12 plants are irritant crops, including, for example, other plants used to prepare exudates such as coffee, cacao beans, tea, mate, tea, and other stimuli Sex plants are included.

  Group 13 plants are tobacco and gum and other plants, including, for example, vegetable oils, insecticides, tobacco, natural rubber, natural gums, other used in the perfume industry, food industry and other industries Resins as well as plant waxes are included.

  In some embodiments, the present invention involves the treatment of any plant other than citrus (ie, any plant that does not belong to the citrus genus). In other embodiments, the practice of the invention is limited to the treatment of plants other than citrus. Independently, in some embodiments, all of the plants to be treated are not plants belonging to the genus Tobacco.

  In some embodiments, the compositions of the invention are used to treat crop plants that grow in a field. Such a processing operation may be performed once or twice or more for a specific crop plant group during one growth period. In some embodiments, the amount of cyclopropene used in a single treatment is 0.1 gram / ha (g / ha) or more, or 0.5 g / ha or more, or 1 g / ha or more. Or 5 g / ha or more, or 25 g / ha or more, or 50 g / ha or more, or 100 g / ha or more. Independently, in some embodiments, the amount of cyclopropene used in a single spray operation is 6000 g / ha or less, or 3000 g / ha or less, or 1500 g / ha or less. Embodiments in which harvested plant parts are processed are also contemplated.

  In some embodiments, the compositions of the present invention include one or more metal complexing agents. A metal complexing agent is a compound containing one or more electron donor atoms that can form coordinate bonds with metal atoms. Some metal complexing agents are chelating agents. As used herein, a “chelating agent” is a compound containing two or more electron donor atoms that can form coordinate bonds with a metal atom, and such chelating agents. Only one molecule can form two or more coordination bonds with one metal atom. In some embodiments, one or more chelating agents are used. In some embodiments, no metal coordinating agent that is not a chelating agent is used.

  In embodiments where one or more chelating agents are used, suitable chelating agents include, for example, organic and inorganic chelating agents. Suitable inorganic chelating agents include, for example, phosphates such as tetrasodium pyrophosphate, sodium tripolyphosphate and hexametaphosphoric acid. Suitable organic chelating agents include chelating agents having a macrocyclic structure and chelating agents having a non-macrocyclic structure.

  Some suitable organic chelating agents having a non-macrocyclic structure include, for example, aminocarboxylic acids, 1,3-diketones, hydroxycarboxylic acids, polyamines, amino alcohols, aromatic heterocyclic bases, phenols, aminophenols Oximes, Schiff bases, sulfur compounds and mixtures thereof. In some embodiments, the chelating agent includes one or more amino carboxylic acids, one or more hydroxy carboxylic acids, one or more oximes, or mixtures thereof. Some suitable aminocarboxylic acids include, for example, ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), N-dihydroxyethylglycine (2-HxG), ethylenebis ( Hydroxyphenylglycine) (EHPG) and mixtures thereof. Some suitable hydroxycarboxylic acids include, for example, tartaric acid, citric acid, gluconic acid, 5-sulfoslicylic acid and mixtures thereof. Some suitable oximes include, for example, dimethylglyoxime, salicylaldoxime, and mixtures thereof. In some embodiments, EDTA is used.

  The use of the metal complexing agent in the present invention is as necessary. In some continuous water embodiments, one or more metal complexing agents are used. In some continuous water embodiments, no metal complexing agent is used. In some continuous oil embodiments, no metal complexing agent is used.

  For the purposes of this specification and claims, unless stated otherwise, when a value is stated to be “from X to Y (X to Y)”, the value is X or greater. And should likewise be understood to mean Y or less.

  For the purposes of this specification and claims, unless a compound is specifically stated otherwise, when a compound is described as being the result of a particular chemical reaction, such description is It should be understood that it is intended to describe the structure of the compound regardless of whether it is produced by that particular chemical reaction. For example, a “fatty alcohol ethoxylate” is a compound whose structure can be understood by assuming an ethoxylation process performed on the fatty alcohol, and such a compound is produced by the process of ethoxylation of the fatty alcohol. Or may be manufactured by a different process.

  For the purposes of this specification and claims, it should be understood that various operations are performed at 25 ° C. in the atmosphere at a pressure of 1 atmosphere, unless specifically stated otherwise.

  For the purposes of this specification and claims, it should be understood that the range and ratio limits recited herein may be combined. For example, if the range 60-120 and the range 80-110 are listed for a particular parameter, it is understood that the range 60-110 and the range 80-120 are also contemplated. As a further independent example, if a particular parameter is disclosed as having a suitable minimum value of 1, 2 and 3, then that parameter is disclosed as having a suitable maximum value of 9 and 10. If so, all of the following ranges are contemplated: 1-9, 1-10, 2-9, 2-10, 3-9, and 3-10.

  Thickeners that can be incorporated into the provided suspension compositions include such ingredients that thicken the composition or increase the viscosity of the composition. Thickeners that can be used in the provided suspension compositions include such ingredients shown in the art as viscosity control agents.

  Examples of thickeners include cellulosic thickeners such as hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose and carboxymethylcellulose. Other examples of thickeners include cellulose gums, alkanetriols; acrylates; substituted celluloses such as hydroxyethylcellulose, carboxymethylcellulose, methylcellulose and hydroxypropylcellulose; cetyl alcohols; gums such as natural or synthetic gums; Long chain alcohols such as alcohols having from about 9 to about 24 carbon atoms; polyglycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene propylene glycol or mixtures thereof; waxes such as natural Includes waxes or synthetic waxes; hardened oils; glycol esters; fatty acid esters; long chain acids; acid amides; silicates; Further suitable thickeners include organoclays, where such organoclays react the hydrophilic clay with a quaternary ammonium compound so that the hydrophilic clay becomes organophilic. Thus, it can be made from natural smectite clay, hectorite clay or montmorillonite clay by making it compatible with non-aqueous media.

  In one embodiment, suitable thickeners include polymeric thickeners that are addition polymers of unsaturated carboxylic acids and / or anhydrides. Examples of polymeric thickeners include polyacrylates, polyalkyl acrylates, polymethacrylates and maleic anhydride. These polymeric thickeners have an average molecular weight range from about 500,000 to about 2 million, or from 1 million to 4 million.

  In another embodiment, suitable thickeners are as disclosed in US Pat. No. 5,373,044 and US Patent Application Publication US2009 / 0253862A, the contents of which are hereby incorporated by reference. Also included are copolymers of acrylates and methacrylates, or copolymers of acrylic acid and alkyl methacrylates. The provided suspension compositions can have a viscosity from about 50 mPas to about 50,000 mPas, or from 500 mPas to about 15,000 mPas.

  Suitable polymeric thickeners include natural rubber, polypropylene, polyisoprene, polybutadiene, poly (styrene-butadiene), poly (ethylene-propylene-diene), polyurethane, polymethacrylate, polyisobutylene, poly (isobutylene-succinic acid). ), Poly (isobutylene-succinic acid-polyacrylamide), polyurea and polyethylene. In some embodiments, the polymeric thickener includes a first component and a second component, provided that the first component has a weight average molecular weight greater than the second component. For example, the polymeric thickener comprises a high molecular weight component and a low molecular weight component, (1) a propylene polymer (copolymer or homopolymer) having a weight average molecular weight exceeding 200.000, and (2) a weight average molecular weight of 200. Characterized in that it comprises a mixture of propylene polymers (copolymers or homopolymers) that are less than .000.

  In another embodiment, the polymeric thickener comprises a high molecular weight component comprising a polymer of propylene (copolymer or homopolymer) having a weight average molecular weight of at least 200.000 or 200.000 to 350.000. A low molecular weight component comprising a propylene polymer (copolymer or homopolymer) having a weight average molecular weight of less than 100.000 or 50.000 to 100.000. The weight ratio of the high molecular weight component to the low molecular weight component in the polymeric thickener is 1:40 to 3: 1, 1:40 to 1: 1, 1:40 to 1: 5, 1:25 to 1:15. Or 1:18 to 1:20.

  In one embodiment, the low molecular weight component is a polypropylene homopolymer, i.e. having a melt flow rate between 500 dg / min and 1500 dg / min, or between 750 dg / min and 1250 dg / min, as determined by testing ASTM D1238L. Contains certain polypropylene homopolymers. In further or alternative embodiments, the low molecular weight component comprises a polypropylene homopolymer. In another embodiment, the high molecular weight component has a melt flow rate (ASTM D-1238) of 1.5-15, 1.5-7, or 3-5. In further or alternative embodiments, the high molecular weight component comprises a polypropylene homopolymer or a propylene / ethylene copolymer.

  In another embodiment, a composition comprising an oil medium, wherein the particles are suspended in the oil medium, the particles comprise cyclopropene and a molecular encapsulating agent, and the particles are measured by a maximum size. A composition having a median size of 50 micrometers or less is provided.

  In one embodiment, the oil medium includes one or more dispersants. In another embodiment, the oil medium comprises one or more nonionic surfactants. In another embodiment, the oil medium comprises one or more nonionic surfactants having an HLB value of 3-4 and one or more nonionic surfactants having an HLB value of 8-10. And a surfactant. In another embodiment, the oil medium is in the form of droplets suspended in water. In another embodiment, the oil medium forms a continuous medium of the composition. In another embodiment, the particles have a median aspect ratio of 20 or less.

  In another aspect, there is provided a process for treating a plant or plant part comprising contacting a composition provided herein with the plant or plant part. In another embodiment, a process for forming a composition comprising producing a mixture comprising a cyclopropene complex, an oil and a dispersion into a media mill; and milling the mixture to produce the cyclohexane Forming a particle comprising a propene complex, wherein the particle has a median size of 300 micrometers or less, or 200 micrometers or less, or 50 micrometers or less, as measured by maximum length. Provided.

  In another embodiment, a composition comprising a solid particle of a cyclopropene complex comprising a cyclopropene molecule or a portion of a cyclopropene molecule encapsulated in a molecular encapsulating agent, further comprising an oil medium, wherein the solid particle comprises the oil Compositions are provided that are characterized in having a median size of 50 micrometers or less when suspended in a medium and the solid particles are measured by maximum size.

In one embodiment, the oil medium includes one or more dispersants. In another embodiment, the molecular encapsulating agent is alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin or a mixture thereof. In another embodiment, the cyclopropene molecule has a structure of the following formula:

Wherein R is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkylalkyl group, phenyl group or naphthyl group; the substituent is independently halogen, alkoxy Or substituted or unsubstituted phenoxy.

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

In another embodiment, the cyclopropene molecule has a structure of the following formula:

In the formula, R ¹ is a substituted or unsubstituted C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkenyl group, C ₁ -C ₄ alkynyl group, C ₁ -C ₄ cycloalkyl group, cycloalkylalkyl. A group, a phenyl group or a naphthyl group, and R ² , R ³ and R ⁴ are hydrogen. In a further embodiment, the cyclopropene comprises 1-methylcyclopropene (1-MCP).

  In another embodiment, the oil medium comprises one or more nonionic surfactants. In another embodiment, the oil medium comprises one or more nonionic surfactants having an HLB value of 3-4 and one or more nonionic surfactants having an HLB value of 8-10. And a surfactant. In another embodiment, the oil medium is in the form of droplets suspended in water. In another embodiment, the oil medium forms a continuous medium of the composition. In another embodiment, the particles have a median aspect ratio of 20 or less.

The materials used in the examples below were:
Complex 1 = 1 A dry powder containing a complex of 1-MCP and alpha-cyclodextrin, which contains 3.8% 1-MCP by weight. The median size is over 100 micrometers when measured by maximum size. The median aspect ratio is greater than 50.
Oil P1 = paraffin oil containing an arylalkyl ethoxylate surfactant, which is obtained from the Whitmile Micro-Gen Company.
Oil P2 = paraffin oil, which is obtained from Petro Canada Company.
Brij ™ 30 = surfactant: obtained from Croda (ethylene oxide) ₄ lauryl ether (HLB 9.7)
Silwet ™ L-77 = Surfactant: Nonionic silicone obtained from OSi Specialties (HLB 5-8)
Atlox ™ 4914 = dispersant: block copolymer of poly (ethylene oxide) and alkyd resin obtained from Croda (HLB 6)
EDTA = ethylenediaminetetraacetic acid, sodium salt Atsurf ™ 595 = surfactant: glycol monooleate (HLB 3.8) from Croda Company
Dyne-Amic ™ oil = a highly purified methylated vegetable oil blend in combination with an organosilicone surfactant, which is obtained from Helena Chemicals.
Oil emulsion 1 = 0.38 parts by weight of Dyne-Amic ™ oil added to 99.62 parts by weight of water and stirred Rizo ™ oil = emulsifiable methylated soybean oil obtained from Rizobacter Company SoyGold ™ 1100 = methylated soybean oil obtained from Ag Environmental Products Company

Example 1
Preparation of Formulation B The following ingredients were added to the media mill:
292.4 g of oil P1
102.0 g of Complex 1
5.6 g Atlox ™ 4914

  The mixture of ingredients was processed in a media mill until the median particle size was measured by maximum size to be less than 2 micrometers.

Example 2
Preparation of Formulation C The following ingredients were added to the media mill:
194.2 g of oil P2
175.0 g of Complex 1
6.0 g of Brij ™ 30
18.0 g of Silwet ™ L-77
6.8 g Atlox ™ 4914
The mixture of ingredients was processed in a media mill until the median particle size was measured by maximum size to be less than 2 micrometers.

Example 3
Preparation of Formulation D The following ingredients were added to the media mill:
200.4 g of Soy Gold 1100
180.0 g of Complex 1
10.0 g of Silwet ™ L-77
4.0 g Atlox ™ 4914
5.6 g EDTA
The mixture of ingredients was processed in a media mill until the median particle size was measured by maximum size to be less than 2 micrometers.

Example 4
1-MCP retention The ability of a formulation to retain 1-MCP was determined by spraying the spray mixture from a standard spray nozzle and collecting the spray liquid at 18 inches from the spray nozzle and spray nozzle. The resulting liquid was captured in a sealed container and evaluated by analyzing for 1-MCP by analyzing the headspace gas by gas chromatography. Headspace gas chromatography was performed as described in US Patent Application Publication No. 2005/0261132. The first and last unsprayed parts are also analyzed to determine the amount lost to spraying and the amount lost to headspace during the spraying operation.

The spray formulation “Comparative SF-A4” was a mixture of the oil emulsion 1 and the composite 1. Spray formulation “SF-B4” was formulation B, which was added to the water. Each spray formulation contained 100 mg / L 1-MCP and was sprayed from a TeeJet ™ XR8002VS nozzle at a pressure of 138 kPa (20 psi). The results are shown in Table 1.

  Table 1 shows that the oil formulation provides much better performance than the tank mix of 1-MCP complex and oil and also helps to keep 1-MCP in an unsprayed liquid.

Example 5
Biological efficacy The efficacy of the formulation is sprayed onto tomato plants in the greenhouse, the tomato plants are exposed to ethylene, and the upregulation (ie leaf flexion / curvature) response specifically caused by ethylene is evaluated. evaluated.

  1-MCP treated plants and controls were placed in SLX controlled atmosphere shipping boxes and sealed. Ethylene was injected into the box through a septum, resulting in a concentration of 14 ppm. Plants were kept sealed in the dark with ethylene in the atmosphere for 12-14 hours. When the ethylene treatment was finished, the box was opened and scored for upper prevalence. The results are reported as the angle of the leaves relative to the stem, where a value of 50 degrees is typical for unaffected leaves and 120 degrees is the angle of the leaves completely bent by the action of ethylene. .

  The spray formulation “Comparative SF-A51” was 99.99 parts by weight of Oil Emulsion 1 and 0.0132 parts by weight of Complex 1. Comparative SF-A2 was sprayed onto the plants to give a 1-MCP ratio of 1 g / Ha. The spray formulation “Comparative SF-A52” was 99.17 parts by weight of oil emulsion 1 and 0.132 parts by weight of Complex 1. Comparative SF-A2 was sprayed onto the plants to give a ratio of 1-MCP of 10 g / Ha.

The spray formulation “SF-C51” was 0.0279 parts by weight of Formulation C and 99.97 parts by weight of water. SF-C51 was sprayed onto the plants to give a 1-MCP ratio of 1 g / Ha. The spray formulation “SF-C52” was 0.279 parts by weight of Formulation C and 99.72 parts by weight of water. SF-C52 was sprayed onto the plants to give a 1-MCP ratio of 10 g / Ha.

  The leaf angle reveals that the oil formulations SF-C51 and SF-C52 are more effective than the comparative formulation in counteracting the effects of ethylene.

Example 6
Crop yield enhancement The efficacy of the formulation was evaluated in an outdoor application on soybean. The measure of efficacy was increased yield.

  The spray formulation “Comparative SF-A6” was prepared as follows. 98.97 parts by weight of water were mixed with 1 part by weight of Rizo ™ oil in a spray tank, and then 0.0329 parts by weight of Complex 1 were mixed with the mixture in the spray tank. The spray rate was chosen to give 25 g / Ha 1-CMP in 200 L / Ha water containing 2 L / Ha Rizzo oil. Comparative SF-A6 was applied by ground spray.

Sprayable formulation SF-D6 was prepared by mixing 1.25 liters of formulation D with 3.75 liters of Rizo ™ oil. The sprayable formulation SF-D6 was applied by air spraying at a rate of 25 g / Ha 1-MCP in a total oil of 5 L / Ha. Note that no water was used in SF-D6, resulting in a total liquid spray volume of 5 L / Ha. The results are shown in Table 3. Yield is reported as a percentage of the yield obtained from the untreated control.

  SF-D6 increased soy yield significantly more than the comparative formulation.

Example 7
Suspension Formulation Containing Kraton G1702H Kraton G1702H is a linear styrene ethylene / propylene diblock copolymer. 100 g Kraton G1702H is mixed with 1900 g Isopar V and heated to 100 ° C. for 30 minutes with stirring. A clear viscous liquid is formed with 5% solids.

  Similarly, a more transparent but still injectable liquid can be formed with 8% Kraton G1702H in Isopar V. These concentrated solutions can be diluted with additional solvents by simply mixing at room temperature.

  Particularly useful viscosities are found at 2.25% and 2.50% Kraton G1702H in the solvent. Kraton G1702H also includes (1) white mineral oil containing Blandol and Klealol, (2) hydrotreated intermediate petroleum distillate containing Conosol 260, Unipar SH 260CC, Isopar V liquid, and (3) light hydrogenated light It can be dissolved in similar concentrations in petroleum distillates (eg, Unopar SH 210AS, Isopar M solution, etc.). Each of the above compositions can provide a solution with increased viscosity. Vegetable oils (including soybean oil and corn oil) do not show this effect. When 1-methylcyclopropene / α-cyclodextrin complex and / or zeolite / molecular sieve is suspended in concentrated hydrocarbon, if the concentration of Kraton G1702H is 2.0% by weight or more, sedimentation occurs almost. Absent. In addition, a suspension of 10 wt% 1-methylcyclopropene / α-cyclodextrin complex and 3.3 wt% Silipolite NK10AP (4A molecular sieve) in 2.25% Kraton G1702H is 30 psig to 60 psig Can be sprayed as is using a conventional spray nozzle (Spraying Systems TeeJet XR8002 or XR8008) using a standard pressure of

  Polymers that are not suitable as thickeners include: (1) Nordel IP3745P (terpolymer of ethylene propylene norbornadiene): 100 g of Nordel IP3745 mixed with 1900 g of Isopar V, with stirring, 4 Heat to 100 ° C. for hours. None seem to dissolve and no thickening is observed; (2) Septon 1020 (linear styrene ethylene / propylene diblock copolymer): 100 g Septon 1020 mixed with 1900 g Isopar V And with stirring, heat to 100 ° C. for 4 hours. Only slightly soluble but only slight thickening is observed; (3) Septon 1001 (linear styrene ethylene / propylene diblock copolymer): 1900 g Isopar from 100 g Septon 1001 Mix with V and heat to 100 ° C for 4 hours with stirring. Only very little dissolves, but some (but insufficient) thickening is observed.

Claims (31)

A composition comprising an oil medium and at least one thickener,
A composition wherein the composition is a suspension of solid particles in the oil medium, and the solid particles comprise a cyclopropene compound and a molecular encapsulating agent.   The composition of claim 1, wherein the suspension does not settle for at least 2 weeks.   The composition of claim 1, wherein the oil medium is selected from the group consisting of white mineral oil, hydrotreated intermediate petroleum distillate, hydrotreated light petroleum distillate, and combinations thereof.   The composition of claim 3, wherein the white mineral oil comprises Blandol and / or Klearol.   4. The composition of claim 3, wherein the hydrotreated middle petroleum distillate comprises Conosol 260, Unipar SH 260CC, and / or Isopar V.   4. The composition of claim 3, wherein the hydrotreated light petroleum distillate comprises Unipar SH 210AS and / or Isopar M. The cyclopropene compound has the following formula:

Wherein R is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkylalkyl group, phenyl group or naphthyl group; the substituent is independently halogen, Alkoxy or substituted or unsubstituted phenoxy)
The composition of claim 1, wherein _8. The composition of claim 7, wherein R is _C1-8 alkyl.   8. A composition according to claim 7, wherein R is methyl. The cyclopropene compound has the following formula:

Wherein R ¹ is a substituted or unsubstituted C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkenyl group, C ₁ -C ₄ alkynyl group, C ₁ -C ₄ cycloalkyl group, cycloalkyl An alkyl group, a phenyl group or a naphthyl group, and R ² , R ³ and R ⁴ are hydrogen)
The composition of claim 1, wherein   The composition of claim 1, wherein the cyclopropene compound comprises 1-methylcyclopropene (1-MCP).   The composition of claim 1, wherein the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, and combinations thereof.   The composition of claim 1, wherein the molecular encapsulating agent comprises alpha-cyclodextrin.   The composition of claim 1, wherein the solid particles comprise at least 10% by weight of the composition.   The composition of claim 1 comprising at least 10% by weight of a complex of 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin.   The composition of claim 1, comprising at least 1% by weight of the at least one thickener.   The composition of claim 1, wherein the at least one thickener comprises a cellulosic thickener.   The composition of claim 1, wherein the at least one thickener comprises a polymeric thickener.   19. The composition of claim 18, wherein the polymeric thickener is formed from at least one of an acrylate, an alkyl acrylate, and an anhydride.   The polymeric thickeners are polypropylene, polyisoprene, polybutadiene, poly (styrene-butadiene), poly (styrene-ethylene / propylene), poly (ethylene-propylene-diene), polyurethane, polymethacrylate, polyisobutylene, poly 19. The composition of claim 18, comprising at least one component selected from the group consisting of (isobutylene-succinic acid), poly (isobutylene-succinic acid-polyacrylamide), polyurea, polyethylene, and combinations thereof.   19. The composition of claim 18, wherein the polymeric thickener comprises a first component and a second component, wherein the first component has a weight average molecular weight greater than the second component. .   24. The composition of claim 21, wherein the weight ratio of the first component to the second component is at least 1: 5.   The composition of claim 21, wherein the polymeric thickener does not comprise an ethylene / propylene / norbornadiene copolymer.   The composition of claim 21, wherein the polymeric thickener does not comprise a styrene / ethylene / propylene copolymer. A method for preparing a suspension composition comprising:
(A) placing a complex comprising cyclopropene and a molecular encapsulant, an oil medium and a material comprising at least one thickener in a media mill; and (b) milling said material into a composition comprising solid particles. A method comprising.   26. The method of claim 25, wherein the suspension composition does not settle for at least 2 weeks.   26. The method of claim 25, wherein the cyclopropene comprises 1-methylcyclopropene (1-MCP).   26. The method of claim 25, wherein the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, and combinations thereof.   26. The method of claim 25, wherein the molecular encapsulating agent comprises alpha-cyclodextrin.   26. The method of claim 25, wherein the solid particles comprise at least 10% by weight of the composition.   26. The method of claim 25, wherein the composition comprises at least 10% by weight of a complex of 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin.