阅读说明：本技术 高负荷吡氟氯禾灵酯组合物 (haloxyfop-R-methyl composition with high load ) 是由 R·阿科斯塔·阿马多 N·维托拉齐·德·卡斯特罗 H·全 于 2019-01-03 设计创作，主要内容包括：本文提供了高负荷的乳油组合物,其含有至少875g/L的吡氟氯禾灵酯、溶剂和表面活性剂。所述乳油组合物在5℃下倾倒后留下少于3.9重量百分比的残余物。(Provided herein are high-load emulsifiable concentrate compositions containing at least 875g/L of haloxyfop-methyl, a solvent, and a surfactant. The emulsifiable concentrate composition leaves less than 3.9 weight percent residue after pouring at 5 ℃.)

1. An emulsifiable concentrate comprising:

(a) at least about 875g/L haloxyfop-methyl in grams acid equivalent per liter (gae/L);

(b) one or more solvents; and

(c) one or more surfactants;

wherein the emulsifiable concentrate leaves less than 3.9 weight percent residue after pouring at 5 ℃.

2. The emulsifiable concentrate of claim 1 wherein the haloxyfop-methyl is at a concentration of at least about 900g/L in grams acid equivalent per liter.

3. An emulsifiable concentrate as claimed in claim 1 or 2 wherein the haloxyfop-methyl is (R) -haloxyfop-methyl.

4. An emulsifiable concentrate as set forth in any one of claims 1-3 wherein said one or more solvents is selected from the group comprising: propylene glycol ethers, ethylene glycol ethers, fatty acid methyl esters, propionic acid esters, lactic acid esters, alcohols and dialkylbenzenes.

5. The emulsifiable concentrate as set forth in any one of claims 1-4 wherein said one or more surfactants is selected from the group consisting of: anionic surfactants and nonionic surfactants or mixtures thereof.

6. The emulsifiable concentrate of claim 5 wherein the anionic surfactant is selected from the group consisting of: calcium linear alkyl benzene sulfonate and sodium alkyl sulfosuccinate.

7. The emulsifiable concentrate of claim 5 wherein the nonionic surfactant is selected from the group consisting of: polyoxyalkylene fatty alcohol ethers, polyoxyalkylene alkyl ethers, tributylphenol ethoxylate, and tridecyl alcohol ethoxylate.

8. The emulsifiable concentrate as set forth in any one of claims 1-7 wherein said one or more solvents is selected from the group consisting of:

i. propylene glycol ethers of formula I

Wherein R is₁Is H, methyl or acetyl, and R₂Is C₁-C₃Alkyl or 2-methoxypropan-1-yl;

a glycol ether having the formula II

Wherein R is₃Is C₁-C₆An alkyl group;

fatty acid methyl esters having the formula III

Wherein R is₄Is C₅-C₁₁An alkyl group;

propionate esters having formula IV

Wherein R is₅Is H or OCH₂CH₃And R is₆Is C₁-C₄An alkyl group; and

v. dialkylbenzenes of the formula V

Aliphatic C in the form of D-and/or L-lactate, linear or branched₁-C₁₈Alkyl lactic acid esters

vii.C₂-C₁₂Straight or branched chain alcohols.

9. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises a compound having the formula II wherein R is₃Is C₁-C₆An alkyl group, and the nonionic surfactant is a polyoxyalkylene fatty alcohol ether.

10. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises a compound having the formula I wherein R is₁Is H and R₂Is C₁-C₃An alkyl group, and the nonionic surfactant is a polyoxyalkylene fatty alcohol ether.

11. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises a compound having the formula I wherein R is₁Is H and R₂Is C₁-C₃An alkyl group, the nonionic surfactant is a polyoxyalkylene alkyl ether, and the anionic surfactant is calcium alkyl benzene sulfonate.

12. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises a compound having the formula I wherein R is₁Is H and R₂Is a 2-methoxypropan-1-yl group and the nonionic surfactant is a polyoxyalkylene fatty alcohol ether.

13. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises a compound having the formula I wherein R is₁Is H and R₂Is C₁-C₃An alkyl group, and the nonionic surfactant is a polyoxyalkylene fatty alcohol ether.

14. Milk according to claim 8An oil, wherein the solvent comprises a compound having formula I, wherein R₁Is acetyl and R₂Is C₁-C₃An alkyl group, the nonionic surfactant is a polyoxyalkylene alkyl ether, and the anionic surfactant is calcium alkyl benzene sulfonate.

15. An emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises one or more dialkylbenzene compounds, said nonionic surfactant is a polyoxyalkylene fatty alcohol ether, and said anionic surfactant is calcium alkylbenzene sulfonate.

16. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises a compound having the formula IV wherein R is₅Is H and R₆Is C₁-C₄An alkyl group, and the nonionic surfactant comprises at least one polyoxyalkylene fatty alcohol ether and a tridecyl alcohol ethoxylate.

17. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises a compound having the formula IV wherein R is₅Is OCH₂CH₃And R is₆Is C₁-C₄An alkyl group, and the nonionic surfactant comprises at least one polyoxyalkylene fatty alcohol ether and a tridecyl alcohol ethoxylate.

18. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises wherein R₅Is H and R₆Is C₁-C₄A compound of formula IV of an alkyl group, and wherein R₃Is C₁-C₆A compound having the formula II of an alkyl group, and the surfactant comprises at least one polyoxyalkylene fatty alcohol ether and a blend of anionic and nonionic surfactants.

19. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises wherein R₅Is H and R₆Is C₁-C₄Alkyl radicalOf formula IV, and C₂-C₁₂A linear or branched alcohol, and the surfactant comprises at least one polyoxyalkylene fatty alcohol ether and a blend of anionic and nonionic surfactants.

20. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises wherein R₅Is H and R₆Is C₁-C₄A compound of formula IV of the alkyl group, and a linear or branched aliphatic C in the form of D-andor L-lactate₁-C₁₈An alkyl lactate ester, and the surfactant comprises at least one polyoxyalkylene fatty alcohol ether and a blend of anionic and nonionic surfactants.

21. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises wherein R₅Is H and R₆Is C₁-C₄A compound of formula IV of the alkyl group, and a linear or branched aliphatic C in the form of D-andor L-lactate₁-C₁₈An alkyl lactate, and the surfactant comprises at least one polyoxyalkylene fatty alcohol ether and sodium alkyl sulfosuccinate.

22. The emulsifiable concentrate as set forth in claim 8 wherein said solvent comprises a compound having the formula IV wherein R is₅Is H and R₆Is C₁-C₄An alkyl group, and the surfactant comprises at least one polyoxyalkylene fatty alcohol ether, sodium alkyl sulfosuccinate, and tributylphenol ethoxylate.

23. The emulsifiable concentrate of claim 1 further comprising a co-solvent.

24. An emulsifiable concentrate as set forth in claim 1 wherein said emulsifiable concentrate has a viscosity of less than 6.7 pascal-seconds (pa.s) at a temperature of-5 ℃.

25. An emulsifiable concentrate as set forth in claim 24 wherein said emulsifiable concentrate has a viscosity of less than 5pa.s at a temperature of-5 ℃.

26. An emulsifiable concentrate as set forth in claim 25 wherein said emulsifiable concentrate has a viscosity of less than 4pa.s at a temperature of-5 ℃.

27. An emulsifiable concentrate as set forth in claim 26 wherein said emulsifiable concentrate has a viscosity of less than 3pa.s at a temperature of-5 ℃.

Technical Field

The present disclosure includes high-load haloxyfop-ethyl compositions having reduced viscosity and/or improved pourability and methods of use thereof. Such compositions are useful, for example, when used at low temperatures.

Background

Development and use of high-load, liquid agrochemical formulations is an important innovation, reducing pest control costs by reducing packaging costs, increasing shipping efficiency, reducing container cleaning costs, and reducing the amount of solvent used in the formulation (both cost and potential environmental impact are reduced). However, the development of these formulations is not without challenges, such as low solubility of the active ingredient, high viscosity (especially at low temperatures), insufficient storage stability, and tank-mix issues. Haloxyfop, e.g. (R) -haloxyfop-methyl, is currently sold as a 520 gram acid equivalent per liter (gae/L) emulsifiable concentrate (emulisifiable concentrate) formulation, but if the concentration can be increased substantially, additional value can be found through the cost savings and reduction of environmental impact mentioned above.

The recently registered high-load products containing 900gae/L of (R) -haloxyfop-methyl exhibit a viscosity at-5 ℃ of more than 11 pascal-seconds (Pa.s) which greatly exceeds the viscosity of the 520gae/L products currently on the market (0.16 Pa.s). Such viscosity increases can make handling and application of the product challenging when used at low temperatures. High load (R) -haloxyfop-methyl formulations with lower viscosity will improve usability at low temperatures.

Accordingly, there is a need for high load haloxyfop formulations having lower viscosity and/or pourability to improve the ability to use such formulations.

Disclosure of Invention

Provided herein are high-load emulsifiable concentrate compositions containing at least about 875gae/L haloxyfop-methyl, one or more solvents, and one or more surfactants. The emulsifiable concentrate composition leaves less than 3.9 weight percent residue after pouring at 5 ℃.

Detailed Description

I. Active ingredient

As used herein, haloxyfop-methyl may be understood to include all haloxyfop-methyl esters, such as esters having the structure:

wherein R is C₁-C₆Alkyl groups, and chiral carbons (labeled with;) may be enriched in the (R) -enantiomer; or may be enriched in a racemic mixture containing equal amounts of the (R) -and (S) -enantiomers.

For example, (R) -haloxyfop-methyl (I) has the following structure:

the compounds of formula I can also be identified by The name (R) -methyl 2- [4- (3-chloro-5-trifluoromethyl-2-pyridinyloxy) phenoxy ] propionate, and their properties and uses have been described in "The Pesticide Manual" handbook for pesticides ", 12 th edition (2000), page 499 and 501, which is incorporated herein by reference. The compounds of formula (I) have a chiral carbon atom that exists predominantly in the (R) -configuration (which is the predominant enantiomer in commercial products). Exemplary uses of compounds having formula I include controlling undesirable vegetation in a variety of non-crop and crop settings, including primarily grassy weeds.

The described high load (R) -haloxyfop-methyl Emulsifiable Concentrate (EC) compositions include at least about 900 grams acid equivalent per liter (gae/L) of (R) -haloxyfop-methyl (I). As used herein, at least about 900 grams acid equivalent per liter (gae/L) of (R) -haloxyfop-methyl refers to (R) -haloxyfop-methyl (I) of at least 875gae/L, at least 880gae/L, at least 885gae/L, at least 890gae/L, at least 895gae/L, at least 900gae/L, at least 905gae/L, at least 910gae/L, at least 915gae/L, at least 920gae/L, or at least 925 gae/L.

Solvent III

High-load herbicidal Emulsifiable Concentrates (EC) compositions containing (R) -haloxyfop-methyl (I) also contain one or more solvents and one or more surfactants.

Solvents used in high load emulsifiable concentrates may include the following:

a) a propylene glycol ether having the formula I:

wherein R is₁Is H, methyl or acetyl, and R₂Is C₁-C₃Alkyl or 2-methoxypropan-1-yl. Compounds having formula I include propylene glycol monomethyl ether acetate (as Dowanol)^TMPMA or Eastman^TMAvailable as PM acetate), 1-propoxypropan-2-ol (available as Dowanol)^TMAvailable as PnP or Huntsman PP), dipropylene glycol dimethyl ether (available as Proglyde)^TMAvailable as DMM), and methoxy isopropanol (available as Dowanol)^TMPM、Eastman^TMPM and HuntsmanPM).

b) A glycol ether having the formula II:

wherein R is₃Is C₁-C₆An alkyl group. Compounds having formula II include 2-propoxyethanol (as propyl Cellosolve)^TM、Eastman^TMAvailable from EP and Huntsman EP) and 2- (hexyloxy) ethanol (as hexyl Cellosolve)^TMAvailable).

c) Fatty acid methyl esters having the formula III:

wherein R is₄Is C₅、C₇Or C₉A linear alkyl group. Fatty acid methyl esters having formula III and mixtures thereof are included asC-25 and Agnique ME 610.

d) A propionate having formula IV:

wherein R is₅Is H or OCH₂CH₃And R is₆Is C₁-C₄An alkyl group. Compounds having formula IV include propyl, butyl and pentyl esters of propionic acid (R)₅＝H；R₆＝C₂-C₄Alkyl), and ethyl ester of 3-ethoxypropionic acid (R)₅＝OCH₂CH₃；R₆＝CH₃(ii) a Referred to as UCAR^TMEster EEP), all available from Dow as UCAR^TMThe solvent is available.

e) A dialkylbenzene having the formula V:

the dialkylbenzenes having formula V include xylenes, such as ortho-, meta-, and para-xylene, and mixtures thereof.

f) Alkyl lactate: suitable alkyl lactate esters may include aliphatic C1-C18 alkyl lactate esters (particularly C6-C10 alkyl lactate esters), which may be straight or branched chain. Examples are cyclohexyl lactate, 2-ethylhexyl lactate, 2-methylcyclohexyl lactate, heptyl lactate, octyl lactate or mixtures thereof. Particularly preferred is 2-ethylhexyl lactate. The alkyl lactate may be present in the form of D-and or L-lactate, L-lactate being preferred.

g) An alcohol; the alcohol under consideration is preferably C₂-C₁₂Alkanols, such as ethanol, propanol, hexanol, octanol and dodecanol. The alcohol may be linear or branched, such as 2-ethylhexanol and isotridecanol. Can be present in the form of diols or triols, such as ethylene glycol, propylene glycol, dipropylene glycol and 2-methyl-2, 4-pentanediol. According to different aspects, it is likewise possible to use cyclic alcohols, preferably cyclopentanol and cyclohexanol.

In addition, mixtures of any of the compounds and solvents described herein can provide acceptable solvents for the described emulsifiable concentrates.

The high-load herbicidal emulsifiable concentrate can include from about 10 weight percent (wt%) to about 20 wt% of a solvent or solvent mixture. In some embodiments, the high-load herbicidal emulsifiable concentrate can include from about 10 wt% to about 18 wt%, from about 10 wt% to about 16 wt%, from about 10 wt% to about 15 wt%, from about 11 wt% to about 15 wt%, from about 12 wt% to about 14 wt% of the solvent or solvent mixture relative to the total composition.

Surfactant IV

High-load herbicidal emulsifiable concentrates containing (R) -haloxyfop-methyl (I) require the use of at least one emulsifying surfactant. Suitable emulsifying surfactants may be selected from nonionic and anionic surfactants or commercial blends thereof.

Suitable nonionic surfactants can include surfactant groups including polyoxyalkylene fatty alcohol ethers (e.g., such as Tensiofix) and related products thereof^TM96DB08 and Tensiofix^TM97DB03 (Ajinomoto Omnichem), polyoxyalkylene alkyl ethers (e.g. like Termul)^(R)203(Huntsman)), alkanol ethoxylates (e.g. like Makon)^(R)TD-18 (Stepan), tributylphenol ethoxylate (e.g. like Sapogenat)^(R)T080 (Clariant))), ethoxylated castor oils (e.g. like Toximal^(R)8242 (spandex)).

Tensiofix^TM96DB08 contains a polyoxyalkylene fatty alcohol ether surfactant (e.g., a fatty alcohol alkoxylate or polyalkylene glycol fatty alkyl ether) which is an EO-PO copolymer ether prepared from a fatty alcohol, ethylene oxide (oxetane) and propylene oxide (methyloxetane). The fatty alcohol may include one or more C₁₂-C₁₅Straight or branched, fully saturated carbon chains, and the EO (ethylene oxide) and PO (propylene oxide) units may be arranged randomly or in blocks in the copolymer chain. Examples of the fatty alcohol may include, for example, lauryl alcohol (e.g., 1-dodecanol), tridecyl alcohol (e.g., 1-tridecyl alcohol), myristyl alcohol (e.g., 1-tetradecyl alcohol), pentadecyl alcohol (e.g., 1-pentadecanyl alcohol), and mixtures thereof.

Termul^(R)203 contains a polyoxyalkylene alkyl ether surfactant (e.g., alcohol alkoxylate or polyalkylene glycol)Alkyl ethers) which are EO-PO polymers prepared from butanol, ethylene oxide (oxetane) and propylene oxide (methyloxetane) and are available in Chemical Abstracts]In chemical registration systems are referred to as: oxetane (oxairane), methyl oxetane, oxetane-containing polymer, monobutyl ether (CAS No. 9038-95-3). Termul^(R)203 has an HLB (hydrophilic lipophilic balance) value of 17.5. The HLB value is an empirical expression of the relationship of the hydrophilic ("water-loving") and hydrophobic ("hydrophobic") groups of a surfactant.

Makon^(R)TD-18 contains a tridecyl alcohol ethoxylate surfactant having an average of 18 EO units per molecule and an HLB value of 16.

Sapogenat^(R)T080 is a tri-sec-butylphenol polyglycol ether with an average of 8 moles of ethoxylation.

Toximul^(R)8242 is an ethoxylated castor oil with an average of 40 moles of ethoxylation.

For example, suitable anionic surfactants include sulfosuccinates (e.g., such as Aerosol)^(R)OT-S (Solvay)), calcium alkylbenzenesulfonate (optionally in a liquid solvent carrier, e.g., like Ninate^(R)60E (Spilan), also available from other suppliers, such as Nansa^(R)EVM 70/2E (Innospec), Agnique^(R)ABS 60-C EH (BASF)).

Ninate^(R)60E contained a 60 wt% solution of calcium dodecylbenzenesulfonate in 2-ethylhexanol.

Aerosol^(R)OT-S (Solvay) is dioctyl sodium sulfosuccinate, also available from other suppliers, such as Triton from Dow Chemical^TMGR-7M。

There are also suitable commercially available blends of anionic and nonionic surfactants, such as Atlox^TMAL 3307 (mila).

The amount of the at least one emulsifying surfactant included in the high-load herbicidal emulsifiable concentrate can range from about 1 wt% to about 20 wt%, from about 5 wt% to about 15 wt%, from about 5 wt% to about 13 wt%, from about 5 wt% to about 10 wt%, from about 5 wt% to about 8 wt%, relative to the total composition.

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula II (wherein R is₃A linear propyl group) and a nonionic surfactant which is a polyoxyalkylene fatty alcohol ether.

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula I (wherein R is₁Is H and R₂Is C₁-C₃Alkyl group), and a nonionic surfactant which is a polyoxyalkylene fatty alcohol ether.

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula I (wherein R is₁Is H and R₂Is C₁-C₃Alkyl group), a nonionic surfactant which is a polyoxyalkylene alkyl ether, and an anionic surfactant which is calcium alkyl benzene sulfonate.

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula I (wherein R is₁Is H and R₂2-methoxypropan-1-yl), and a nonionic surfactant which is a polyoxyalkylene fatty alcohol ether.

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula I (wherein R is₁Is H and R₂Is C₁-C₃Alkyl group), and a nonionic surfactant which is a polyoxyalkylene fatty alcohol ether.

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula I (wherein R is₁Is acetyl and R₂Is C₁-C₃Alkyl group), a nonionic surfactant which is a polyoxyalkylene alkyl ether, and an anionic surfactant which is calcium alkyl benzene sulfonate.

The high-load herbicidal emulsifiable concentrate composition described herein can comprise a solvent composed of one or more dialkylbenzene compounds including one or more of the group consisting of o-xylene, m-xylene and p-xylene, a nonionic surfactant which is a polyoxyalkylene fatty alcohol ether, and an anionic surfactant which is calcium alkylbenzene sulfonate.

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula IV (wherein R is₅Is H and R₆Is C₁-C₄Alkyl group or ethyl group), and a nonionic surfactant (including at least one polyoxyalkylene fatty alcohol ether and a tridecyl alcohol ethoxylate).

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula IV (wherein R is₅Is OCH₂CH₃And R is₆Is C₁-C₄Alkyl group or methyl group), and a nonionic surfactant (including at least one polyoxyalkylene fatty alcohol ether and a tridecyl alcohol ethoxylate).

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula IV (wherein R is₅Is H and R₆Is C₁-C₄An alkyl group or a linear propyl group), and a nonionic surfactant (including at least one polyoxyalkylene fatty alcohol ether and a tridecyl alcohol ethoxylate).

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula IV (wherein R is₅Is H and R₆Is C₁-C₄An alkyl group or a straight chain butyl group), and a nonionic surfactant (including at least one polyoxyalkylene fatty alcohol ether and a tridecyl alcohol ethoxylate).

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula IV (wherein R is₅Is H and R₆Is C₁-C₄Alkyl group) and compounds having the formula II (wherein R is₃Is C₁-C₆Alkyl), and a surfactant comprising at least one polyoxyalkylene fatty alcohol ether and a blend of anionic and nonionic surfactants.

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula IV (wherein R is₅Is H and R₆Is C₁-C₄Alkyl radical) and C₂-C₁₂A solvent consisting of a linear or branched alcohol, and a surfactant comprising at least one polyoxyalkylene fatty alcohol ether and a blend of anionic and nonionic surfactants.

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula IV (wherein R is₅Is H and R₆Is C₁-C₄Alkyl radical) and linear or branched aliphatic C in the form of D-and/or L-lactates₁-C₁₈An alkyl lactate ester, and a surfactant (comprising at least one polyoxyalkylene fatty alcohol ether and a blend of anionic and nonionic surfactants).

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula IV (wherein R is₅Is H and R₆Is C1-C₄Alkyl radical) and linear or branched aliphatic C in the form of D-and/or L-lactates₁-C₁₈An alkyl lactate ester, and a surfactant (comprising at least one polyoxyalkylene fatty alcohol ether and sodium alkyl sulfosuccinate).

The high-load herbicidal emulsifiable concentrate compositions described herein can comprise a mixture of compounds having the formula IV (wherein R is₅Is H and R₆Is C1-C₄Alkyl group), and a surfactant (comprising at least one polyoxyalkylene fatty alcohol ether, sodium alkyl sulfosuccinate, and tributylphenol ethoxylate).

Viscosity IV

The viscosity of the high-load herbicidal emulsifiable concentrate compositions described herein is an important physical property to measure to assess the effectiveness of the compositions in their intended use. Important aspects of the composition relating to viscosity include low temperature viscosity, such as, for example, viscosity at temperatures below about-5 ℃, below about 0 ℃, below about 5 ℃, below about 10 ℃, below about 20 ℃. In addition, the viscosity of the emulsifiable concentrate composition can affect pourability, emulsion formation, emulsion viscosity or adhesion to the walls and/or filters of the application device, as well as emulsion stability. The viscosity of a particular liquid composition may depend on the relative amounts and types of ingredients in the composition and the temperature at which the viscosity is measured.

Because of the large amount of active ingredient present in high-load compositions, there may be less room for other ingredients in certain aspects, and therefore fewer options available for controlling the high viscosity that may be inherent in such compositions. However, in certain aspects, the viscosity at a temperature of-5 ℃ can be as low as 6.7 pascal-seconds (pa.s) or less, as low as 5pa.s or less, as low as 4pa.s or less, as low as 3pa.s or less, or as low as 2pa.s or less.

When using a TA Instruments HR-2Discovery rheometer for 100sec^-1The measured viscosity of the high-load herbicidal emulsifiable concentrates described herein can be less than about 11 pascal-seconds (Pa-sec) at about-5 ℃, less than about 5.2 pascal-seconds (Pa-sec) at about 0 ℃, less than about 2.5 pascal-seconds (Pa-sec) at about 5 ℃, less than about 1.3 pascal-seconds (Pa-sec) at about 10 ℃, or less than about 0.4 pascal-seconds (Pa-sec) at about 20 ℃ when operated at a shear rate of (f) and measured with a stainless steel, 60mm, 2 degree cone axis.

Pourability V. pourability

As previously discussed, the improved pourability of high load haloxyfop formulations can improve the ability to use such formulations in the field. In various aspects, the pourability can be as low as 3.9 weight percent residue or less, 3 weight percent residue or less, or 2 weight percent residue or less, in certain aspects of pourability at a temperature of 5 ℃.

To investigate how to effectively treat high-load emulsifiable concentrates of (R) -haloxyfop methyl ester at different temperatures, a series of samples were tested at 5 ℃ using the CIPAC MT 148 method. According to this method, a sample of the cream is left to stand at 5 ℃ for a defined time and the amount remaining in the test jar (testcylinder) after a standardized pouring method (pouring at 45 degrees for 60 seconds) and washing with water is determined. Residue After Pouring (RAP) and Residue After Rinsing (RAR) values were obtained as a weight percentage of the initial sample. The results are shown in example 3.

Additional ingredients

The (R) -haloxyfop-methyl (I) -containing high-load herbicidal emulsifiable concentrate compositions described herein can be applied in combination with one or more other herbicides to control a wider range of undesirable vegetation. When used in combination with other herbicides, the compositions can be formulated with the other herbicide(s), tank-mixed with the other herbicide(s), or applied sequentially with the other herbicide(s). Certain herbicides that can be used in conjunction with the compositions and methods described herein include, but are not limited to: 4-CPA, 4-CPB, 4-CPP, 3,4-DA, 3,4-DB, 2,4-DEB, 2,4-DEP, 3,4-DP, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, acetochlor, acifluorfen, aclonifen, alachlor, ethachlor, ethametrafish, diclofop-methyl, pentachloroacetic acid (aloac), azinone (amitridione), ametryn, tebufenozide, amicarbazone, amidosulfuron, primisulfuric acid, aminopyralid, methylaminophos, fenpyroxim, sulfamate, anilofos, asulam, aniluron, benfurazol, flumetsulam, tetrazolium, azid, avenachlor, bcb, fluorobutyryl, benazolin, benfurazolidone, furazolidone, bentazon, bentazone, pyrazosulfuron, and the like, Dicentrazone, bentazone sodium, fenfluramine, bensulfuron methyl, benoxacor, pyroxaflufen, neodelphine, thifenuron, bialaphos, flurtamone, benfop-methyl, bialaphos, bispyribac, borax, bromacil, furosemide, bromobutylachlor, bromoxynil, butachlor, butafenacet, butachlor, buthioketone, buthiouron, butralin, butafenacet, clomazone, butate, dimethoate, cafenstrole, calcium chlorate, calcium cyanamide, clofenamate, bensulam, imazamethabenzuron, carbazole, methidathion, carfentrazone-ethyl, CEPC, metofen, mefenapyr, butralin, clodinafop-propargyl, clonidine, clomazone, ethoxysulfuron (chlorentron), valclofenapyr, flufenapyr, fenapyr (Loflumuron), fenapyr (Lophan) and clofenapyr (Lophan), clofenapyr, Chlorpyrifos, chlorimuron-ethyl, cumquat, trichloropropionic acid, chlorsulfuron, oxypyr, chlorpropham, chlorsulfuron, dichlorvos, chloramben, indomethabenzuron, cinmethylin, cinosulfuron, pyroxsulam, clethodim, iodochlordiazate (clinodinate), clodinafop-propargyl (clodinafop-propargyl), chlorobutanol (clohop), clomazone, clomeprop, clofenpropathyrid, clofenac, cyclobutenedione (cloproxydim), cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, chlorphenamine, cresol, prosulfocarb, cyanazine, cyhalofop, cyclosulfate, cyclosulfuron, cyhalofop-butyl, cyhalofop, cyazon, cyhalofop, metolachlor, dichlorfon, clomazone, cloma, Diclofop-methyl, diclosulam, diclofop-methyl, fenoxaprop-ethyl, difloram-ethyl, dimethenamid-p, isoethazine, dimethenamid-p, benoxacor, dimethenamid-p, pyridaben, dimethenamid, dinol, propamol, penitrol, dimethenal, terbufenol, molinate, ipretryn, diquat, sulindac, dithiopyr, dacron, DMPA, DNOC, DSMA, EBEP, cyanazine, soduo, sulfentrazone, EPTC, imazaquin, penflufen, ibuprofenon, ethametsulfuron, thiadiazolyl, benfurazolin, sulfofenpyr, ethoxyfen, EXD, bensulfuron, aldicarb, fenoxaprop-p-ethyl, fenoxaprop-ethyl, sufenoxaprop-p-ethyl, fenoxaprop-p, Clomazone ethyl alcohol (fenteracol), thiazosulfuron, fentrazamide, fensulfuron, fluazifop-butyl, difloram, fluazifop-butyl, florasulam, fluazifop-butyl, isopyrafen, fluoroketosulfuron, fluazifop-methyl, fluazifop-butyl, flufenacet, flupyracet (flufenican), flupyridazinyl-ethyl, flumetsulam, trifluorooxazine (flumezin), flumiclorac, flumioxazin, propyzamide, flumeturon, norflurazon, bifenthrin, bifenox, flusulfuron, flumetoxazole, flupropamol (flupropamol), tetrafluoropropionic acid, fluazifosulfuron, flumetsulam, fludioxonil, flurtamone, metribuzin, fomesafen, formosulfuron, glufosinate, flumiclorac, flumiclorafen, glufosinate, glyphosate salts and esters, nitroflurazone, halosulfuron-methyl, haloxydine (haloxydine), haloxyfop-methyl, fluazifop-methyl, hexachloroacetone, hexafluoroarsonate (hexaflurate), hexazinone (hexazinone), imazamox, imazethapyr, imazapic (imazapic), imazapyr, imazethapyr, imazapyr, imazosulfuron (imazosulfuron), indoxacin (indoofan), indoxachlor (indafllam), ioxynil, iodoxynil, iodomethane, iodometsulfuron-methyl, iodosulfuron-ethyl-sodium, iodosulfuron (iofensulfuron), ioxynil, fenpyrazamide (ipfencarbazone), propamodin (iprodione), cimetidine (isocalol), isoproturon (isoproturon, isoxadifenox, isoxabenone (isoxaben), isoxadifenoxolone (isoxauron, isoxabensulfuron), isoxadifenox, isoxaprop-ethyl-methyl, imazachlor, isoxapyroxim (isoxathiuron), isoproturon (isoxadifenox, isoxaprop-ethyl, isoxabensulfuron, isoxadifenox, isoxaprop-ethyl, isoxabencarb, isoxaprop-ethyl, isoxaben, Isoxaflutole, clomazone, carbendazim, spirodiclofen (ketospiradox), lactofen, cyfluazifop-p-methyl, linuron, MAA, MAMA, 2-methyl-4-chloropropionic acid, dimethomorph, mefenacet, sulfluramid, atrazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, dimethenazone, methabenzthiazuron (methalpropalin), imazazole, methiocarb (methioben), methimazolin (methiozolin), imazamethabenzuron, ethon, gelazine, methyl isothiocyanate, metsulfuron, pyrosulfuron, bromuron, metolachlor, metoxuron, metribuzin, metrazol, metsulfuron-methyl, metosulmetsulfuron-methyl, metolachlor, metosulam, metolachlor, meto, Chloruron, metolachlor, varroa, MSMA, napropamide, alachlor, napropamide, oxasulfuron, nicosulfuron, fluorochloroachlor, sulindac, aclonifen, trifluoromethoxyfen, norflurazon, penoxsulam, pyribensulfuron, sulfamethazine, oxadiargyl, oxadiazon, pyridaben, epoxysulfuron, oxaziclomefone, oxyfluorfen, pyraflufen-ethyl, parafluazuron, paraflurron, paraquat, kephalam, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, mechlorethamine, pentoxazone, perfluorine, petalol, dimethofen, dimethenan, pyroxene, pyroxsulam, phenmedin, phenmedipham, phencyclate, picloram, pyraclonidine, pyraflufen-ethyl, metolachlor, potassium arsenate, pyroxsulam, pretilachlor, propulfen-methyl, meton, propulfocarb, propulfen-ethyl, metolachlor, metolac, Cyazosin (procyazine), propamocarb, flumetsulam, cyflufen, clethodim, ganaphron, prohexadione, prometryn, propyzate, propyzamide, propanil, propyzamide, propyrisulfuron, penoxsulam, methidathion (prosufalin), prosulfocarb, prosulfuron, primidone, clofenapyr, butachlor, idafenon (pyridanon), pyraclonil (pyraclonil), pyraflufen-ethyl, pyrasulfofenpyrad, pyrazoxynil (pyrazogyl), pyraflutole, pyrazosulfuron-ethyl, prosulfocarb, pyribenzoxim, clomedil, clofenpyr, pyridaben (pyrifoil), pyridaben, pyriminobac-ethyl, pyrithiobac, metosulam, metominostrobin, quinacr-ethyl, quinclorac, quin, Thiocyananilide (rhodethanil), rimsulfuron, saflufenacil, S-metolachlor, terbuthylazine, metolachlor, metosulam, sethoxydim, cyclosulfamuron, simatong (simeton), simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, diclosamide, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, azethapyr, imazalil, SYN-523, TCA, sulfenamide, buthiouron, tefurotrimazone, tembotrione, pyroxene, terbufalin, terbuchlor, metoxydim, terbuthylazine, metoxuron, dimethoate, dimethozin, fluazinam, fluometuron (teflucuron), methoxythiazuron, thifluuron, thiazachlor, thiadiazolidin (thiazimin), thidiazuron, thiencarbazone-methyl, thifensulfuron-methyl, penoxsulam, pyrazone, pyrazosulfuron (pyrazosulfuron), pyrazosulfuron-ethyl, pyrazosulfuron-S, thion, thiothiflufen-, Triafamone, triallate, triasulfuron, tribenuron-methyl, dicamba, imazachlor, metribuzin, trifloxysulfuron, trifluralin, triflusulfuron, Trifenoxypropionic acid (trifop), Triflomoxone, trihydroxytriazine, Trimeturon, indanthrone (tripopindan), pradak, Tribenuron, imazamox, xylulam, and salts, esters, optically active isomers, and mixtures thereof.

In some embodiments, the compositions described herein are used in combination with one or more plant growth regulators such as 2,3, 5-triiodobenzoic acid, IAA, IBA, naphthylacetamide, alpha-naphthylacetic acid, benzyladenine, 4-hydroxyphenylethanol, kinetin, zeatin, endothallic acid, pentachlorophenol, thidiazuron, defoliation, ivermectin, ethephon, maleichydrazide, gibberellin, gibberellic acid, abscisic acid, pyrimidinol, glufosinate, glyphosate, isobarinol (isopyramid), jasmonic acid, maleichydrazide, mepiquat, reshapein, dichlorofluoren, pyrimethanil, fluorosulfonamide, paclobutrazol, tetracyclozole, uniconazole, brassinolide-ethyl, cycloheximide, ethylene, sulbencarb, prohexadione, imazalil, and trinexapac-ethyl. In some embodiments, the plant growth regulator is mixed with halauxifen (halauxifen) to produce a preferential beneficial effect on the plant.

The compositions provided herein can further include one or more agriculturally acceptable adjuvants or carriers. Such mixtures may be designed for direct application to the weeds or their locus, or may be designed as concentrates or formulations which are usually diluted with additional carriers and adjuvants prior to application. The adjuvant or carrier may be a solid (such as, for example, a dust, granules, water dispersible granules, or wettable powder), or a liquid (such as an emulsifiable concentrate, solution, emulsion, or suspension). In addition, the adjuvants or carriers may also be provided as a pre-mix or in a tank mix.

Suitable agricultural adjuvants and carriers include, but are not limited to, crop oil concentrates; nonylphenol ethoxylate; benzyl cocoalkyl dimethyl quaternary ammonium salt; a blend of petroleum hydrocarbon, alkyl ester, organic acid, and anionic surfactant; c₉-C₁₁An alkyl polyglycoside; a phosphorylated alcohol ethoxylate; natural primary alcohol (C)₁₂-C₁₆) An ethoxylate; di-sec-butylphenolEO-PO block copolymers; a methyl terminated polysiloxane; nonylphenol ethoxylate + urea ammonium nitrate; an emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8 EO); tallow amine ethoxylate (15 EO); PEG (400) dioleate-99.

Examples of liquid carriers that can be used in the compositions and methods described herein include water and organic solvents. Examples of useful organic solvents include, but are not limited to, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monohydric or dihydric alcohols, trihydric or other lower polyhydric alcohols (containing 4 to 6 hydroxyl groups), such as 2-ethylhexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, dioctyl succinate, adipic acid succinate, dioctyl phthalate, etc.; esters of monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids, and the like. Specific organic solvents include, but are not limited to, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methanol, ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, N-dimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers, and the like. Water may be used as a carrier to dilute the concentrate.

Suitable solid carriers include, but are not limited to, talc, pyrophyllite clay, silica, attapulgite clay, kaolin, diatomaceous earth (kieselguhr), chalk, diatomaceous earth (diatomaceous earth), lime, calcium carbonate, bentonite, Fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, cellulose, and the like.

The compositions described herein may further comprise one or more surfactants. Such surfactants can be used in both solid and liquid compositions, and can be designed to be diluted with a carrier prior to application. Surface activeThe agents may be characterized as anionic, cationic or nonionic, and may be used as emulsifiers, wetting agents, suspending agents or for other purposes. Surfactants which may also be used in the formulations of the present invention are described, inter alia, in the McCutcheon's Detergents and emulsifiers Annual notes]MC Publishing Corp [ MC Publishing Co.)]Riqiwood, N.J., 1998 and Encyclopedia of Surfactants]Volumes I-III, Chemical Publishing Co. [ Chemical Publishing Co. ]]New York, 1980-81. Surfactants include, but are not limited to, alkyl sulfates, such as diethanolammonium lauryl sulfate; alkyl aryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, e.g. nonylphenol-C₁₈An ethoxylate; alcohol-alkylene oxide addition products, e.g. tridecyl alcohol-C₁₆An ethoxylate; soaps, such as sodium stearate; alkyl naphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium di (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethyl ammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of mono-and dialkyl phosphates; vegetable or seed oils, such as soybean oil, rapeseed/canola oil, olive oil, castor oil, sunflower oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, and the like; and esters of the above vegetable oils, such as methyl esters. Such materials (e.g., vegetable or seed oils and their esters) can be used interchangeably as agricultural adjuvants, as liquid carriers, or as surfactants.

Other additives that may be used in the compositions provided herein include, but are not limited to, compatibilizers, defoamers, chelating agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, sticking agents, dispersing agents, thickening agents, freezing point depressants, biocides, and the like. The compositions may also contain other compatible components, such as other herbicides, plant growth regulators, fungicides, insecticides, and the like, and may be formulated with liquid fertilizers or solid particulate fertilizer carriers (e.g., ammonium nitrate, urea, and the like).

The concentration of active ingredient in the compositions described herein is typically from 0.0005 to 98 weight percent. Additionally, concentrations of 0.0006 to 90 weight percent may be used. In compositions designed for use as concentrates, the active ingredient can be present at a concentration of 0.1 to 98 weight percent or 0.5 to 90 weight percent. Such compositions may be diluted with an inert carrier, such as, for example, water, prior to administration. Diluted compositions typically applied to soil at or near the vegetation may contain 0.0006 to 15.0 weight percent active ingredient or 0.001 to 10.0 weight percent active ingredient.

The following examples are provided to illustrate various aspects of the compositions and methods described herein and should not be construed as limiting the claims.

Examples of the invention

Example 1.High load (R) -haloxyfop-methyl compositions (900gae/L) were prepared with the solvents and surfactants listed in Table 1.

(R) -haloxyfop-methyl ester technical grade material (purity about 97%) was diluted in each of the solvents listed in Table 1, followed by the addition of one or more surfactants to provide compositions 1-39 listed in Table 1 and comparative example A. Comparative example a was prepared using information from patent application AU 2014203147(a 1). The block copolymer should be heated to a liquid state for ease of addition. Homogenization was performed by stirring each sample using a simple stirrer impeller. When tested according to the CIPAC MT 36.3 method, the resulting samples were found to be translucent brown homogeneous solutions with commercially acceptable emulsion properties over a wide range of water hardness.

Table 1A.A sample of 900gae/l of (R) -haloxyfop-methyl ester formulation (amounts are% by weight) containing solvent and surfactant is shown

Table 1B.Shows 90 containing solvent and surfactant0gae/l of a sample of (R) -haloxyfop-methyl ester formulation (amounts are% by weight)

Table 1C.A sample of 900gae/l of (R) -haloxyfop-methyl ester formulation (amounts are% by weight) containing solvent and surfactant is shown

Table 1D.A sample of 900gae/l of (R) -haloxyfop-methyl ester formulation (amounts are% by weight) containing solvent and surfactant is shown

Table 1E.A sample of 900gae/l of (R) -haloxyfop-methyl ester formulation (amounts are% by weight) containing solvent and surfactant is shown

Table 1F.A sample of 900gae/l of (R) -haloxyfop-methyl ester formulation (amounts are% by weight) containing solvent and surfactant is shown

Example 2.The viscosity of the high load (R) -haloxyfop-methyl composition prepared in example 1 was determined.

The viscosity values of the compositions shown in table 1 were determined and are shown in table 2. The viscosity was measured using a TA instruments HR-2Discovery rheometer (equipped with stainless steel, 60mm, 2 degree cone) and reported in pascal-seconds at temperatures of-5 deg.C, 0 deg.C, 5 deg.C, 10 deg.C, 20 deg.C, 30 deg.C, and 40 deg.C.

Table 2.Determination of the viscosity (reported in pascal-seconds) of the 900gae/l (R) -haloxyfop-methyl ester samples prepared in Table 1

Example 3.The pourability (CIPAC MT 148) at 5 ℃ of the various high load (R) -haloxyfop-methyl compositions prepared in example 1 was determined.

To investigate the extent to which high load (R) -haloxyfop-methyl ester formulations were processed at low temperature, the pourability of a series of samples was tested at 5 ℃ using the CIPACMT 148 method. Briefly, the method involves measuring the amount of material remaining in the container after a standardized pouring method (60 seconds of pouring at a 45 degree angle). The container was then rinsed with water and the amount of material remaining in the container after the second pour was determined.

TABLE 3For high load (R) -haloxyfop-methyl compositions compared to comparative example A¹The pourability test of (2) yields a Residue After Pouring (RAP) value and a Residue After Rinsing (RAR) value-using CIPAC MT 148 at 5 ℃

The scope of the invention is not limited by the various embodiments or aspects disclosed herein, which are intended as illustrations of several aspects, and any embodiments that are functionally equivalent are within the scope of the invention. Various modifications of the compositions and methods in addition to those shown and described herein will be apparent to those skilled in the art and are intended to fall within the scope of the appended claims. Moreover, although only certain representative combinations of the composition ingredients and method steps disclosed herein are specifically discussed in the above examples, other combinations of the composition ingredients and method steps will be apparent to those skilled in the art and are also intended to fall within the scope of the appended claims. Thus, combinations of components or method steps may be specifically mentioned herein; however, other combinations of components and method steps are included, even if not explicitly stated. The terms including and variations thereof as used herein are used synonymously with the terms including and variations thereof and are open, non-limiting terms.