HK1081400A - Pesticide formulations containing alkoxylated amines - Google Patents

Description

Pesticide formulations comprising alkoxylated amines

no marking

The present invention relates to compositions comprising pesticides, in particular formulations for increasing the biological activity effect of plant protection agents (acaricides, bactericides, fungicides, herbicides, insecticides, molluscicides, nematicides and rodenticides).

Plant protection agents are chemical or natural substances that penetrate into plant cells, plant tissues or parasites in or on plants and damage or destroy them.

The herbicide is the largest proportion in the pesticide after the pesticide and the bactericide.

Most important herbicides are chemical substances that affect the transport system of plants, for example, inhibiting photosynthesis, fatty acid biosynthesis or amino acid biosynthesis, resulting in the inhibition of germination and growth of plants until death.

Known pesticides, for example herbicides of the N- (phosphonomethyl) glycine (glyphosate) class. Glyphosate has good tolerance to the environment, is a highly effective and widely used herbicide, and has been used in large quantities in agriculture. It is preferably used as a water-soluble salt, for example as an alkali metal salt, ammonium salt, alkylamine salt, alkylsulfonium salt, alkylphosphonium salt, sulphonamide salt or aminoguanidine salt, or even as a free acid in the form of a liquid or solid formulation, together with a wetting agent, applied to the plant foliage and weeds, acting on the transport system of the plants and destroying them.

The biological activity of a pesticide is determined by the time of activity and the concentration of activity in view of damage to the plant caused by plant growth or the action of the active ingredient on the leaves or via the roots. The general problem is that only a small fraction of the active agent exerts the desired activity, and the vast majority is lost without its effect.

This ecological and economic disadvantage can be reduced by adding surface-active adjuvants to the pesticide formulation.

As disclosed in WO 99/05914, an increase in the effectiveness of anionic pesticides can be achieved by preparing aqueous colloidal dispersions of anionic actives and protonated polyamines or derivatives thereof.

US 5750468 teaches that the concentration of glyphosate can be reduced without diminishing its biological activity by adding tertiary or quaternary ether amines to the pesticide formulation.

Alkoxylated primary ether amines as claimed in US 5616811, and their complimentary wetting, emulsifying and surfactant properties.

However, the development of new pesticidal compositions or pesticidal formulations with improved activity, while being economical, easy to use and well tolerated by humans and the environment, remains a goal to be pursued.

Surprisingly, this object can be achieved by including certain alkoxylated amines in the pesticide composition in addition to the pesticide.

The present invention relates to a composition comprising

a) One or more pesticides and

b) one or more compounds selected from formula I

R-N{(A¹O)_rH}-(CH₂)₃-N{(A²O)_sH}-[(CH₂)₃-N{(A³O)_tH}]_x-(A⁴O)_uH (I)

Wherein

R is a linear or branched alkyl or alkenyl radical having from 6 to 30 carbon atoms, preferably having from 8 to 19 carbon atoms, particularly preferably a tallow radical,

A¹to A⁴Each independently is-G₂H₄-or-C₃H₆-a group of,

r, s, t and u are each independently 1 to 400,

the sum of the numbers of r, s, t and u is from 10 to 600, preferably from 100 to 400,

and

x is 1 to 10.

In the context of the present invention, the compounds of the formula I also comprise derivatives in which one or more nitrogen atoms have no free electron pair, but in which a fourth group Q is attached to these nitrogen atoms, which group is selected from H and linear or branched alkyl groups having from 1 to 6 carbon atoms, in particular H or methyl, before and after the compounds of the formula I have been described. Different groups Q may be attached to different nitrogen atoms in the compound. In compounds containing one or more of such groups Q, the nitrogen atom to which the group Q is attached carries a positive charge. The corresponding counter-ion P may be selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate, carbonate, bicarbonate, phosphate, mono-and dihydrogenphosphate, pyrophosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methanesulfonate or ethanesulfonate, or from the group consisting of anionic compounds of the formula: r⁶SO₃ ^-、R⁷SO₄ ^-Or R⁶COO^-Wherein R is⁶And R⁷Is straight-chain or branched C₈-C₂₀Alkyl, preferably C₁₀-C₁₈Alkyl radical, furthermore R⁷May also be C₇-C₁₈An alkyl phenyl group. The structural unit is as follows a simple QP shapeShown in the formula.

Thus, corresponding derivatives of the compounds of the formula I can be described in a simplified manner, for example of the formula Ia

R-N{Q¹P¹}{(A¹O)_rH}-(CH₂)₃-N{Q²P²}{(A²O)_sH}-[(CH₂)₃-N{Q³P³}{(A³O)_tH}]_x-(A⁴O)_uH

(Ia)

Wherein

R、A¹To A⁴R, s, t, u and x are as defined above,

Q¹、Q²and Q³Each independently is H or a linear or branched alkyl group having 1 to 6 carbon atoms, and

P¹、P²and P³Each independently selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate, carbonate, bicarbonate, phosphate, mono-and dihydrogenphosphate, pyrophosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methanesulfonate or ethanesulfonate, or from an anionic compound of the formula: r⁶SO₃ ^-、R⁷SO₄ ^-Or R⁶COO^-Wherein R is⁶And R⁷Is straight-chain or branched C₈-C₂₀Alkyl, preferably C₁₀-C₁₈Alkyl radical, furthermore R⁷May also be C₇-C₁₈An alkyl phenyl group.

Mention may be made, for example, as preferred radicals P, of dodecyl sulfate and cumene sulfate.

In the compounds of the formula I, the radical R is preferably a coconut or tallow radical.

Preferred alkoxylated amines of the formula I are those in which

R is an alkyl group having 8 to 19 carbon atoms, especially a tallow group.

A¹To A⁴Each independently is-C₂H₄-or-C₃H₆-a group of,

r, s, t and u are each independently 1 to 400,

the sum of the numbers r, s, t and u is from 10 to 600, preferably from 100 to 400, and particularly preferably from 250 to 350,

and is

x is 1 or 2.

In the alkoxylated amines of formula I, the polyalkoxy group is a polyethoxy or polypropoxy polymer, or an ethylene oxide/propylene oxide (EO/PO) block copolymer or an EO/PO random copolymer. Within a chain, there may be 1 to 400 EO or PO or EO/PO units in a statistical distribution. In general, the compounds of the formula I may comprise EO or PO or EO/PO units of from 10 to 600, preferably from 100 to 400, particularly preferably from 250 to 350.

Surprisingly, the alkoxylated amines of formula I can be prepared into solid and liquid pesticide formulations having excellent solubility in water. Another performance advantage of use is the high phase stability of highly concentrated liquid formulations made from anionic pesticides (especially glyphosate salt forms), optionally agrochemical salts and alkoxylated amines of formula I. When the alkoxylated amine is added, the ionic component does not crystallize out even during a relatively long storage period.

In addition to high electrolyte stability, the use of the adjuvants according to the invention shows an improvement in compatibility and an improved bioactivity of the active ingredient on plants.

The alkoxylated amines of the formula I used in the pesticide formulations as adjuvants according to the invention are prepared in a multistage synthesis, for example as shown below.

Placing a primary alkylamine, e.g. cocoamine or tallowamine, under N in the presence or absence of a catalyst₂At a temperature of from 40 ℃ toAcrylonitrile is metered in at 90 ℃ in a molar ratio of amine to nitrile of from 1: 0.95 to 1: 1.20 over a period of from 1 to 2 hours. The reaction is exothermic. After the addition was complete, the mixture was stirred at the reaction temperature for 2 to 6 hours. The nitrile formed is washed first with dilute sodium hydroxide solution and subsequently with water. The nitrile is hydrogenated with a suitable catalyst, such as Raney nickel, at from 70 ℃ to 120 ℃ in the presence of ammonia and a hydrogen pressure of from 150 to 180 bar to constant pressure under standard conditions (shaking high-pressure treatment). After filtering the content of the autoclave, the amine obtained is distilled under a water-jet vacuum.

To prepare the alkoxylated amines of the formula I, the amines are reacted again in a similar manner with acrylonitrile and hydrogenated. The obtained triamine can be converted into tetramine or the like by further reacting with acrylonitrile and subsequently hydrogenating.

For the alkoxylation, the dried polyamine is placed in N in the absence or presence of a suitable basic catalyst, such as NaOH, at from 140 to 200 ℃₂And the alkoxylation is carried out in a 2-step process. In the process, ethylene oxide and/or propylene oxide are gradually increased up to the extent required for the alkoxylation (number of amines). The post-reaction amounts are dependent on the alkylene oxide and are carried out for 1 to 3 hours, respectively.

The corresponding derivatives of the compounds of the formula I, in which one or more radicals Q are bonded to one or more nitrogen atoms, of the compounds of the formula Ia can be prepared, for example, by methods known to those skilled in the art from compounds of the formula I, for example by appropriate reaction of the compounds of the formula I with HCl or methyl chloride.

The alkoxylated amines of the formula I are suitable according to the invention as adjuvants in pesticide formulations for increasing the biological activity of herbicides, insecticides, fungicides, acaricides, bactericides, molluscicides, nematicides and rodenticides. In a preferred embodiment, the compound is added to a herbicide formulation. Suitable herbicides are, without the invention being restricted thereto, acifluorfen, asulam, benazolin, bentazone, bialaphos, bromacil, bromoxynil, mefenpyr, clopyralid, 2, 4-D, 2, 4-DB, dalapon, dicamba, 2, 4-dichlopropionic acid, diclofop, endothall, vax, fenoxaprop, fluazifop, imidoxyacetic acid, fluoroglycofen, fomesafen, phosphinothricin, glufosinate, fluazifop, imazapic, imazethapyr, imazaquin, imazethapyr, ioxynil, 2-4-chloro-butyric acid, 2-4-chloropropionic acid, cacodynamic acid, picloram, quinclorac, 2, 3, 6-TBA and TCA.

Preferred pesticides are herbicides of the N- (phosphonomethyl) glycine (glyphosate) class. Among glyphosate, the free acid and especially the water soluble salts are preferred. Secondly, among the water-soluble salts, alkali metal salts, ammonium salts, alkylamine salts, alkylsulfonium salts, alkylphosphonium salts, sulfonamide salts or aminoguanidine salts are preferable. Herein, "alkylamine" is particularly preferably "isopropylamine".

The amount of the compound of formula I in the pesticidal formulation of the present invention may vary over a wide range. The following formulations are preferred.

The concentrated formulations (ready-to-use or natural compositions ("build-in" Zusammensetzng)) which are diluted before use preferably comprise the pesticide in an amount of from 5 to 60% by weight, particularly preferably from 20 to 40% by weight, and the compounds of the formula I in an amount of from 5 to 50% by weight. The amounts are based on the total amount of the concentrate formulation.

Alternatively, the formulations of the present invention may be prepared in solid form, such as a powder, pellet, tablet or granule, which is dissolved in water prior to use. The solid formulations comprise the pesticides preferably in an amount of 20 to 80% by weight, particularly preferably 50 to 75% by weight, particularly preferably 60 to 70% by weight, and the compounds of the formula I preferably in an amount of 5 to 80% by weight, particularly preferably 30 to 60% by weight. The amounts are based on the total amount of the solid preparation.

The invention therefore relates to the use of the following compositions for controlling and/or combating weeds

a) One or more pesticides and

b) one or more compounds selected from formula I

R-N{(A¹O)_rH}-(CH₂)₃-N{(A²O)_sH}-[(CH₂)₃-N{(A³O)_tH}]_x-(A⁴O)_uH (I)

Wherein

R is a linear or branched alkyl or alkenyl group having 6 to 30 carbon atoms,

A¹to A⁴Each independently is-C₂H₄-or-C₃H₆-a group of,

r, s, t and u are each independently 1 to 400,

the sum of the numbers of r, s, t and u is from 10 to 600,

and is

x is a number from 1 to 10,

and wherein the compounds of the formula I also include derivatives in which the fourth radical is attached to one or more nitrogen atoms, which radical is selected from H and straight-chain or branched alkyl radicals having from 1 to 6 carbon atoms, and whose counter-ion is selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate, carbonate, bicarbonate, phosphate, mono-and dihydrogenphosphate, pyrophosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methanesulfonate or ethanesulfonate, or from the group consisting of anionic compounds of the formula: r⁶SO₃ ^-、R⁷SO₄ ^-Or R⁶COO^-Wherein R is⁶And R⁷Is straight-chain or branched C₈-C₂₀Alkyl, preferably C₁₀-C₁₈Alkyl radical, furthermore R⁷May also be C₇-C₁₈An alkyl phenyl group.

The pesticide or pesticides and the compound or compounds of the formula I can also be present here in the form of so-called "tank-mix" compositions. In such compositions, the pesticide or pesticides and the one or more compounds of formula I are all disposed separate from each other. Both compositions are mixed with each other prior to administration, usually shortly before use. In the "tank mix" process, the pesticide is preferably placed in water or an organic solvent, for example an aromatic or aliphatic hydrocarbon such as toluene, xylene or Solvesso, a halogenated hydrocarbon such as tetrachloromethane, trichloromethane, dichloromethane or dichloroethane, or a methylated oil such as the methyl ester of soybean oil or rapeseed oil, before mixing. In the "tank mix" process, the compound of formula I is preferably placed in the material or water prior to mixing. In a preferred embodiment, the pesticide or pesticides and the compound or compounds of formula I are both placed in water.

The concentration of the pesticide or pesticides in the spray mixture is preferably from 0.001 to 10% by weight, particularly preferably from 0.025 to 3% by weight, and particularly preferably from 0.025 to 2% by weight, based on the total amount of the spray mixture. The concentration of the compound or compounds of the formula I in the spray mixture is preferably from 0.01 to 10% by weight, particularly preferably from 0.1 to 2% by weight, and particularly preferably from 0.2 to 1% by weight, based on the combined spray mixture. The ratio of adjuvant to pesticide in the spray mixture is preferably from 1: 10 to 500: 1, particularly preferably from 1: 4 to 4: 1.

The formulations of the present invention may contain thickeners, anticoagulants, antifreezes, solvents, dispersants, emulsifiers, preservatives, other adjuvants, binders, antifoams, diluents, disintegrants, and wetting agents. Xanthan gum and/or cellulose, for example carboxy, methyl, ethyl or propyl cellulose, can be used as thickeners in amounts of 0.01 to 5% by weight, based on the final composition, suitable solvents being monopropylene glycol, animal oils and mineral oils. Suitable dispersants and emulsifiers are nonionic, amphoteric, cationic and anionic surfactants. Preservatives which may be used are organic acids and esters thereof, for example ascorbic acid, ascorbyl palmitate, sorbate, benzoic acid, methyl and propyl 4-hydroxybenzoate, propionate, phenols such as 2-phenylphenate, 1, 2-benzisothiazolin-3-one, formaldehyde, sulfurous acid and salts thereof. Suitable antifoams are silicone polymers. Other adjuvants may be polyglycerols, alcohol ethoxylates, alkyl polysaccharides, fatty amine ethoxylates, sorbitan and sorbitol ethoxylate derivatives and derivatives of alk (en) ylsuccinic anhydrides. The mixing ratio of these auxiliaries to the alkoxylated amines of the formula I according to the invention can be in the range from 1: 10 to 10: 1. Suitable binders for solid preparations are polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, sugars such as sucrose, sorbitol, or starch. Suitable diluents, absorbents or carriers are carbon black, tallow, kaolin, aluminum stearate, calcium or magnesium stearate, sodium tripolyphosphate, sodium tetraborate, sodium sulfate, silicates and sodium benzoate. Effective disintegrants are celluloses such as carboxymethylcellulose, polyvinylpyrrolidone, sodium or potassium acetate, carbonates, bicarbonates, sesquicarbonates, ammonium sulphate or potassium hydrogen phosphate. Humectants that can be used are alcohol ethoxylates/propoxylates.

The high stability of the pesticide formulations of the present invention having alkoxylated amines of formula I in liquid media, even at high pesticide concentrations, is a significant performance advantage.

In a particularly preferred embodiment, the pesticide formulation according to the invention comprises, in addition to the active ingredient and the alkoxylated amine or amines of the formula I, an agrochemical salt, preferably an ammonium salt, particularly preferably ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium thiocyanate and/or ammonium chloride.

The formulations of the present invention may be used in conventional manner. The liquid and solid formulations are diluted with the corresponding amount of water before use.

From 0.1 to 5kg, preferably from 0.3 to 2.5kg, of pesticide per hectare is applied. The proportion of the auxiliaries according to the invention is in the range from 0.002 to about 1.0 kg/ha. The amount of the prepared agricultural chemical preparation for spray application is preferably 50 to 1000l/ha, but may be 10 to 50l/ha for a special application method such as controlled drop application.

Claims (14)

1. A composition comprising

a) One or more pesticides and

b) one or more compounds selected from formula I

R-N{(A¹O)_rH}-(CH₂)₃-N{(A²O)_sH}-[(CH₂)₃-N{(A³O)_tH}]_x-(A⁴O)_uH (I)

Wherein

R is a linear or branched alkyl or alkenyl group having 6 to 30 carbon atoms,

A¹to A⁴Each independently is-C₂H₄-or-C₃H₆-a group of,

r, s, t and u are each independently 1 to 400,

the sum of the numbers of r, s, t and u is from 10 to 600,

and is

x is 1 to 10

And wherein the compounds of the formula I also include derivatives thereof in which the fourth group is attached to one or more nitrogen atoms, this group being selected from H and straight-chain or branched alkyl groups having from 1 to 6 carbon atoms, and the counter-ion of this derivative being selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono-and dihydrogenphosphate, pyrophosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methanesulfonate or ethanesulfonate, or from the group consisting of anionic compounds of the formula: r⁶SO₃ ^-、R⁷SO₄ ^-Or R⁶COO^-Wherein R is⁶And R⁷Is straight-chain or branched C₈-C₂₀Alkyl radical, furthermore R⁷May also be C₇-C₁₈An alkyl phenyl group.

2. Composition according to claim 1, characterized in that the pesticide or pesticides are selected from the group consisting of N- (phosphonomethyl) glycine (glyphosate) type substances.

3. Composition according to claim 2, characterized in that glyphosate is present in the form of the free acid or alkali metal salt, ammonium salt, alkylamine salt, alkylsulfonium salt, alkylphosphonium salt, sulphonamide salt or aminoguanidine salt.

4. Composition according to one or more of claims 1 to 3, characterized by comprising a compound of the formula I, in which

R is an alkyl group having 8 to 19 carbon atoms,

A¹to A⁴Each independently is-C₂H₄-or-C₃H₆-a group of,

r, s, t and u are each independently 1 to 400,

the sum of the numbers of r, s, t and u is from 10 to 600,

and is

x is 1 or 2.

5. Composition according to one or more of claims 1 to 4, characterized in that R is a tallow radical.

6. Composition according to one or more of claims 1 to 5, characterized in that it is present in the form of a concentrated formulation which is diluted before use and comprises 5 to 60% by weight of pesticide and 5 to 50% by weight of one or more compounds of the formula I.

7. Composition according to one or more of claims 1 to 5, characterized in that it is present in the form of a solid preparation which is dissolved with water before use and comprises 20 to 80% by weight of pesticide and 5 to 80% by weight of one or more compounds of the formula I.

8. Composition according to one or more of claims 1 to 5, characterized in that it is present as a spray mixture and comprises 0.001 to 10% by weight of pesticide and 0.01 to 10% by weight of one or more compounds of the formula I.

9. Composition according to one or more of claims 1 to 8, characterized by comprising an agrochemical salt, preferably an ammonium salt.

10. Composition according to claim 9, characterized in that the agrochemical salt is selected from ammonium sulphate, ammonium nitrate, ammonium phosphate, ammonium thiocyanate and/or ammonium chloride.

11. Use of the following compositions for controlling and/or combating weeds

a) One or more pesticides and

b) one or more compounds selected from formula I

R-N{(A¹O)_rH}-(CH₂)₃-N{(A²O)_sH}-[(CH₂)₃-N{(A³O)_tH}]_x-(A⁴O)_uH (I)

Wherein

R is a linear or branched alkyl or alkenyl group having 6 to 30 carbon atoms,

A¹to A⁴Each independently is-C₂H₄-or-C₃H₆-a group of,

r, s, t and u are each independently 1 to 400,

the sum of the numbers of r, s, t and u is from 10 to 600,

and is

x is a number from 1 to 10,

and wherein the compounds of the formula I also include derivatives thereof in which the fourth group is attached to one or more nitrogen atoms, this group being selected from H and straight-chain or branched alkyl groups having from 1 to 6 carbon atoms, and the counter-ion of this derivative being selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono-and dihydrogenphosphate, pyrophosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methanesulfonate or ethanesulfonate, or from the group consisting of anionic compounds of the formula: r⁶SO₃ ^-、R⁷SO₄ ^-Or R⁶COO^-Wherein R is⁶And R⁷Is straight-chain or branched C₈-C₂₀Alkyl radical, furthermore R⁷May also be C₇-C₁₈An alkyl phenyl group.

12. Use according to claim 11, characterized in that it is applied in a tank mix method.

13. Use according to claim 11, characterized in that the pesticide or pesticides are present in water or an organic solvent and the compound or compounds of the formula I are present in the absence of a solvent or in water and are mixed with one another before application.

14. Use according to claim 13, characterized in that the pesticide or pesticides and the compound or compounds of formula I are present in water.