HK1087593B - Agricultural agents containing copolymers - Google Patents

Description

Agricultural compositions comprising copolymers

The present invention relates to agricultural compositions comprising copolymers obtainable by copolymerisation of glycerol ethers and di-or polycarboxylic acids. The polymers impart improved biological activity to plant growth regulators and pesticides (herbicides, insecticides, fungicides, bactericides, molluscicides, nematicides and rodenticides).

Plant growth regulators control physiological responses such as growth, flowering, cell division, and seed maturation.

Crop protection agents are chemical or natural substances which penetrate plant cells, plant tissues or parasitic organisms in or on plants and destroy and/or destroy them. A large part of the pesticide is a herbicide, followed by an insecticide and a fungicide. The most important herbicides are chemical substances which act on the plant transport system, for example to inhibit photosynthesis, fatty acid biosynthesis or amino acid biosynthesis, and lead to the inhibition of plant germination and growth, or to the death of the plant.

The biological activity of a plant growth regulator or pesticide can be determined on the basis of the plant growth or by the damage to the plant caused by the action of the active ingredient on the leaves as a function of the action time and the effective concentration.

In order to exert optimum pesticidal activity, the pesticide must wet the green leaves and remain on them for a sufficiently long time, or the active substance must penetrate the leaf surface. In this connection, it is a general problem that only a part of the active ingredients exerts the desired activity, i.e., can be applied to harmful plants and gramineous plants and adhere thereto for a sufficiently long time to penetrate the plant cells. While most are lost and remain invalid.

As described in a large number of patent specifications, to compensate for this ecological and economic disadvantage, most aqueous pesticide formulations have adjuvants added to them to improve the wetting, solubility, emulsifying or adsorption behavior of the active substances, and, in addition, the additives can facilitate and increase the penetration of the active substances through the leaf surface into the plants.

DE 3533808 describes the preparation of polyglycerol fatty acid esters and their use in plant protection compositions to reduce the surface tension of aqueous compositions.

EP 539980 likewise describes polyglycerol fatty acid esters, in particular alkoxylated polyglycerol esters as adjuvants in plant protection compositions.

WO 01/08481 favours the use of polyglycerol derivatives for plant protection compositions and describes the herbicidal activity of polyglycerol esters on glyphosate. According to WO 02/089575 and WO 03/000055, better activity of the plant protection composition can be obtained by cross-linking polyglycerol esters with dicarboxylic acids.

However, the best exploitation of the biological activity potential of pesticides and growth regulators has not been fully explored.

It is therefore an object of the present invention to develop new compositions or formulations of growth regulators of herbicides and pesticides, in particular of the N-phosphonomethylglycine (glyphosate) species, with improved activity, which are at the same time economical, easy to handle and well tolerated by humans and the environment. Glyphosate is used in large quantities in agriculture due to its high environmental compatibility and at the same time is a widely applied, highly effective herbicide. Together with the wetting agent, preferably in the form of a water-soluble salt, for example its alkali metal, ammonium, alkylamine, alkylsulfonium, alkyl *, mono (isopropylammonium), mono (trimethylsulfonium), sulfonamide or aminoguanidine salts, or else in the form of a free acid in an aqueous preparation, can likewise be applied in solid form to leaves and grasses, which act on the delivery system of the plants and subsequently destroy them.

Surprisingly, it has been found that the pesticidal activity of the plant protection compositions is significantly improved by the addition of copolymers obtained by copolymerization of polyglycerol ethers and dicarboxylic or polycarboxylic acids, compared to crosslinked polyglycerol esters.

The present invention relates to an agricultural composition comprising:

A) pesticides or plant growth regulators

B) Copolymers prepared from

a) Polyglyceryl ethers

b) One or more dicarboxylic acids and/or polycarboxylic acids,

the polyglyceryl ethers are as defined in formula (I)

Wherein the radical R¹、R²And R³Each of which is the same or different and represents hydrogen, optionally 1 to 3 (C)₁-C₄) -alkyl or (C)₁-C₄) -alkoxy-substituted (C)₁-C₃₀) Alkyl, optionally sulphonated and optionally over 1 to 3 (C)₁-C₄) -alkyl or (C)₁-C₄) -alkoxy-substituted (C)₂-C₃₀) -alkenyl, optionally through 1 to 3 (C)₁-C₄) -alkyl or (C)₁-C₄) Phenyl substituted by alkoxy, optionally with 1 to 3 (C)₁-C₄) -alkyl or (C)₁-C₄) -alkoxy-substituted naphthyl, formula R⁴R⁵N-(CH₂)_y-、HO-(CH₂)_y-、-(AO)_zH、-SO₃H、-SO₃ ^-X⁺、-PO₃H₂、-PO₃ ^2-X⁺、-CR₂-COOR’、-CR₂-COO^-X⁺、-CO-R⁶-COOH、-CO-R⁶-COO^-X⁺、-C(R)₂C(R)₂C(R)₂-N(R)₂、-C(R)₂C(R)₂C(R)₂-N((AO)_zH)₂、-[CH₂CH(O(AO)_zH)CH₂O]_n-R¹A group of (a);

wherein R represents H and/or C₁-C₄-an alkyl group;

r' represents H or (C)₁-C₁₀) Alkyl radicals, (C)₂-C₃₀) -alkenyl, optionally sulphonated;

R⁴and R⁵May be the same or different and represents hydrogen, (C)₁-C₁₀) Alkyl radicals, (C)₂-C₃₀) -alkenyl, optionally sulphonated, or of formula- (AO)_zA H group;

R⁶is represented by (C)₁-C₁₀) Alkylene group, (C)₂-C₃₀) -alkenylene, optionally sulphonated;

X⁺represents Na⁺、K⁺、Ca²⁺Or N (R)⁷)₄ ⁺Wherein R is⁷Represents H or (C)₁-C₁₀) -alkyl, preferably (C)₁-C₄) -an alkyl group;

x represents a number from 0 to 15;

y represents a number from 4 to 6;

z represents a number from 0 to 30, preferably from 1 to 5;

a represents an alkenyl group, preferably-C₂H₄-、-C₃H₆-or-C₄H₈-；

n represents a number from 4 to 40, preferably from 5 to 20, in particular from 10 to 20;

and the designations p1, q1, r1, p2, q2, r2, p3, q3 and r3 represent numerical values from 0 to 500;

provided that

The compound of formula (I) contains a free OH group, and R¹、R²And R³At least one of them represents a hydrocarbon group, preferably (C)₁-C₃₀) -an alkyl group.

Preferably the dicarboxylic acid b) is a dicarboxylic acid of the formula (II)

HOOC-R²-COOH (II)

And/or dicarboxylic acids of the formula (III)

Wherein

R²Is (C)₁-C₄₀) An alkylene bridge, preferably (C)₁-C₁₀) Alkylene, particularly preferably (C)₁-C₄) An alkylene group, or (C)₂-C₂₀) An alkenylene bridge, preferably (C)₂-C₆) Alkenylene, particularly preferably C₂-alkenylene, and

r is one or more groups selected from the group consisting of: h; (C)₁-C₂₀) -alkyl, preferably (C)₁-C₆) Alkyl, particularly preferably (C)₁-C₂) -an alkyl group; (C)₂-C₂₀) -alkenyl, preferably (C)₂-C₆) -an alkenyl group; a phenyl group; a benzyl group; halogen; -NO₂；(C₁-C₆) -an alkoxy group; -CHO or-CO ((C)₁-C₆) -an alkyl group). R in the formula (II)²And may be straight chain or branched. Formula (II) also includes dimeric fatty acids, such as Pripolsbergen.

Particularly preferred dicarboxylic acids b) are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, tartaric acid, malic acid, mucic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid and/or terephthalic acid.

Particularly preferred dicarboxylic acids b) are phthalic acid, isophthalic acid and/or terephthalic acid.

A very particularly preferred dicarboxylic acid b) is phthalic acid.

Tricarboxylic acids such as citric acid, dimeric fatty acids, trimeric fatty acids and polycarboxylic acids may likewise be used for crosslinking the glycerol units.

In a further preferred embodiment of the present invention, the agricultural composition comprises a crosslinked polyglyceryl ether of formula (I), wherein formula (I) comprises-SO₃H、-SO₃ ^-X⁺、-PO₃H₂or-PO₃ ^2-X⁺A group.

The polyglycerol derivative used as an adjuvant in the pesticidal formulation of the present invention is obtained by subjecting glycerol to a polycondensation reaction under alkaline conditions, followed by a reaction with a fatty alcohol and crosslinking with a dicarboxylic acid.

For this, glycerol was heated at 200 ℃ and 280 ℃ under alkaline conditions. With the removal of the condensation water, polyglycerols having an average degree of condensation of 3 to 35 glycerol units form in 5 to 15 hours. The resulting polyglycerin and the fatty alcohol or fatty alcohol derivative are heated for 5 to 10 hours in the presence of an acidic catalyst such as sulfuric acid at 120 to 170 ℃ under removal of condensed water. The reaction is controlled by determining the hydroxyl number, which is typically between 400 and 1000mg KOH/g after the reaction is complete.

Subsequently, the above product is reacted with a dicarboxylic acid at 160 ℃ to 200 ℃ for 1 to 3 hours to obtain a crosslinked polyglyceryl ether.

According to the present invention, it is advantageous to modify the polyglyceryl ethers by sulfation, phosphorylation, amination, etc. before or after the crosslinking step which introduces the dicarboxylic acid, using standard methods known to those skilled in the art.

After the reaction mixture was cooled to 60 to 100 ℃, it was diluted with demineralized water to an active ingredient concentration of 40 to 90%, and an alkali metal hydroxide was added so that the pH was 6 to 7.

Particularly preferred are C for polyglycerols having an average degree of condensation n of from 4 to 20, preferably from 6 to 16, particularly preferably from 8 to 10₈-C₂₂Fatty alcohols, preferably C₁₂-C₁₈Fatty alcohols, particularly preferably C₁₂-C₁₄-copolymers crosslinked with phthalic acid after reaction with fatty alcohols. In a particularly preferred embodiment, the free OH groups of the crosslinked polyglycerol ethers are completely or partially sulphated, sulphonated or phosphated.

The copolymers preferably comprise from 0.1 to 30% by weight of structural units originating from component b) and the structural units of component a) make up 100% by weight.

The viscosity of the pure copolymers is preferably from 1000 to 35000mPas, particularly preferably from 1500 to 10000mPas, very particularly preferably from 1500 to 7500mPas, determined with a rotational viscometer at 60 ℃. Higher viscosities are possible, making handling of the material more difficult. Advantageously, the copolymer is processed in a 75% to 90% strength by weight aqueous solution.

As a result of this method of preparation, the polyglyceryl ethers used in the present invention relate to mixtures of compounds of the above formula of different values of n, including unreacted glycerol.

Formulations comprising polyglycerol mixtures, polyglycerol/polyglycerol derivative mixtures and/or polyglycerol derivative mixtures are likewise regarded as pesticide formulations according to the invention.

Highly concentrated aqueous formulations of anionic pesticides, particularly glyphosate in salt form, with crosslinked polyglyceryl ethers are phase stable. After the addition of polyglyceryl ether, the ionic component is not crystallized out even when stored for a long period of time. In addition to being highly stable to electrolytes, the polyglyceryl ethers used in the present invention are also highly stable to hydrolysis and show improved compatibility and contact properties between hydrophilic active ingredients and lipophilic epidermis of plants. The pesticidal formulation of the present invention, which has good wettability and absorption capacity, improves the biological activity of the active ingredient in plants.

According to the invention, polyglycerol ethers are suitable as adjuvants in pesticide formulations for increasing the biological activity of herbicides, insecticides, fungicides, acaricides, bactericides, molluscicides, nematicides and rodenticides, and also for improving the performance of plant growth regulators.

In a preferred embodiment, the polyglycerol derivative is added to a herbicide. Suitable herbicides are especially glyphosate, especially its water-soluble salts, such as alkali metal salts, ammonium salts, alkylamines, alkyl sulfonium salts, alkyl * salts, mono (isopropylammonium salts), mono (trimethylsulfonium salts), sulfonamides or aminoguanidine salts, to which the invention is not limited. Furthermore, the following compounds may also be mentioned: acifluorfen, asulam, benazolin, bentazone, bialaphos, bromacil, bromoxynil, mefenpyr, clopyralid, 2, 4-D, 2, 4-DB, dalapon, dicamba, 2, 4-dichloropropionic acid, diclofop, benzalkonium, fenoxaprop, fluazifop, imidoxyacetic acid, fluoroglycofen, fomesafen, phosphinothricin, glufosinate, fluazifop, imazapic, imazamic acid, imazethapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, 2-4-chloropropionic acid, methyl arsonic acid/MSMA, naproxen, picloram, quinclorac, 2, 3, 6-TBA and TCA.

Examples of preferred embodiments of the copolymerization reaction are described below.

A) Polymerization of glycerol to obtain oligoglycerol or polyglycerol:

the glycerol can be polymerized in a conventional manner at 240 ℃ and 270 ℃ with simultaneous introduction of nitrogen in a stirring apparatus equipped with a dehydrator to give an oligoglycerol or a polyglycerol. The catalyst used was a 50% sodium hydroxide solution with a concentration ranging from 0.1 to 0.4% by weight. After 5 to 20 hours, the polymerization is stopped, depending on the desired degree of polymerization. The sample was removed and the OH number was determined. The OH number can be used to calculate the average molar amount of oligoglycerol or polyglycerol. If desired, the polyglycerol may be alkoxylated by known methods.

B) One-pot method of prepolymerizing polyglycerol (Eintopfverfahren):

in a stirred vessel equipped with a means for azeotropic removal of water (Wasseruskreiser), molten polyglycerol is mixed with a dicarboxylic or polycarboxylic acid and a fatty alcohol or alkoxylated fatty alcohol, or fatty alcohol derivative, in the desired molar ratio and stirred with heating at 200 ℃ and 240 ℃ for 7 hours.

C) The polyglycerol is first copolymerized (cross-linked) with a dicarboxylic acid, and then the product is copolymerized with a fatty alcohol, or an alkoxylated fatty alcohol, or a fatty alcohol derivative:

in a stirring vessel equipped with a means for azeotropic removal of water, molten polyglycerol and dicarboxylic acid or polycarboxylic acid are mixed in a desired molar ratio and stirred under heating at 200-240 ℃ for 2 hours. The resulting product was clear and homogeneous. Subsequently, a fatty alcohol, or an alkoxylated fatty alcohol, or a fatty alcohol derivative is added and esterified at 200-240 ℃ for 5 hours.

D) The polyglycerol is first copolymerized with a fatty alcohol or an alkoxylated fatty alcohol or fatty alcohol derivative, and subsequently copolymerized (crosslinked) with a dicarboxylic or polycarboxylic acid:

in a stirred vessel equipped with means for azeotropic removal of water, the molten polyglycerol was mixed with the fatty alcohol or alkoxylated fatty alcohol or fatty alcohol derivative in the desired molar ratio and stirred under heating at 200-240 ℃ for 5 hours. Subsequently, a dicarboxylic acid or polycarboxylic acid is added in the desired molar ratio and esterified at 200-240 ℃ for 2 hours.

Indeed, the pesticide formulation of the present invention may comprise any concentration of the copolymer.

Particularly preferred formulations are tank mixes and ready-to-use compositions comprising from 0.001 to 10% by weight, preferably from 0.05 to 2% by weight, of the pesticide and from 0.01 to 10% by weight, preferably from 0.1 to 2% by weight, particularly preferably from 0.2 to 1% by weight, of the copolymer. The weight ratio of copolymer to pesticide is preferably between 1: 10 and 500: 1, particularly preferably between 1: 4 and 4: 1.

Concentrated formulations diluted before use may contain from 5 to 60% by weight, preferably from 20 to 40% by weight, of pesticide and from 3 to 50% by weight of copolymer. The weight ratio of copolymer to pesticide here is preferably between 1: 20 and 1: 1, preferably between 1: 10 and 1: 2.

Alternatively, the formulations of the present invention may be prepared in solid form as a powder, pellet, tablet or granule, which is dissolved in water prior to use. The solid formulations may comprise from 20 to 80% by weight, preferably from 50 to 75% by weight, particularly preferably from 60 to 70% by weight, of pesticide and from 5 to 50% by weight, preferably from 10 to 30% by weight, of copolymer.

In addition, the pesticide formulation may contain conventional thickeners, antigelling agents, antifreeze agents, solvents, dispersants, emulsifiers, preservatives, other adjuvants, binders, antifoams, diluents, disintegrants and wetting agents.

Thickeners which may be used are xanthan gum and/or cellulose, for example carboxy cellulose, methyl cellulose, ethyl cellulose or propyl cellulose. The final composition preferably comprises 0.01 to 5 wt% of a thickener. Suitable solvents are monopropylene glycol, animal or mineral oils. Suitable dispersants and emulsifiers are nonionic, amphoteric, cationic and anionic surfactants.

Preservatives can be 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 defoamers are silicone polymers.

Other adjuvants may be fatty alcohol ethoxylates, alkyl polysaccharides, fatty amine ethoxylates, sorbitan ethoxylate derivatives, sorbitol ethoxylate derivatives and derivatives of alk (en) yl succinic anhydride. The mixing ratio of the auxiliary to the copolymer is preferably 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.

Suitable disintegrants are celluloses, such as carboxymethylcellulose, polyvinylpyrrolidone, sodium or potassium acetate, carbonates, bicarbonates, sesquicarbonates, ammonium sulfate or potassium hydrogen phosphate. Wetting agents that may be used are fatty alcohol ethoxylates/propoxylates.

The pesticide formulation preferably has a pH of 4 to 8, particularly preferably 6 to 7.

The formulations of the present invention may be administered in conventional manner.

The aqueous concentrates and solid formulations are diluted with an appropriate amount of water prior to application. Preferably from 0.1 to 5kg, preferably from 0.3 to 2.5kg, of pesticide are applied per hectare. The copolymer portion is preferably from 0.1 to 3.0 kg/ha. The amount of the pesticide preparation sprayed is preferably 50 to 1000 l/ha.

The properties of the copolymer or pesticide formulation, such as solubility in water, stability to electrolytes, viscosity and compatibility with plant protection agents, can advantageously be readily adjusted by the degree of crosslinking. The type and amount of dicarboxylic or polycarboxylic acid component b) determines the degree of crosslinking, the amount being particularly important.

Surprisingly, highly concentrated aqueous formulations of anionic pesticides, particularly glyphosate and copolymers in salt form, have been found to be phase stable. Even under long-term storage, no crystallization of the ionic component was observed. In addition to high stability towards electrolytes, the copolymers used according to the invention lead to improved compatibility and contact properties between hydrophilic active ingredients and the lipophilic epidermis of plants. The pesticidal formulation of the present invention, which has good wettability and absorption capacity, improves the biological activity of the active ingredient in plants.

Examples

Hereinafter, preparation examples of the crosslinked polyglyceryl ether will be described, but the present invention is not limited thereto.

Preparation of polyglycerol with n-9.7:

2000g of glycerol and 6.0g of NaOH (50%) were heated with stirring at 270 ℃ in a stirred vessel equipped with a means for azeotropic removal of water, while passing nitrogen. After 9 hours of reaction and removal of 444g of water, a sample was taken and the OH number was determined. An OH number of 892mgKOH/g was measured. This corresponds to an average degree of condensation n of 9.7 glycerol units. The degree of condensation can also be determined approximately by the viscosity and the refractive index of the reaction mixture. For this, a calibration curve must be prepared in advance.

Preparation of copolymer I

180g of polyglycerol n-9.7 (0.243mol) with 24.3g (0.122mol) of C_12/14Mixing the fatty alcohol. 2% by weight of sulfuric acid (50%) was added as catalyst. Introducing N into a stirring vessel equipped with a means for azeotropic removal of water₂Next, the reaction mixture was heated at 150 ℃ for 7 hours. Subsequently, 4.03g (0.024mol) of phthalic acid were added and heating was continued at 180 ℃ for 2 hours. The hydroxyl number of the product obtained was 770mg KOH/g.

Preparation of copolymer II

180g of polyglycerol n ═ 9.7(0.243mol) and 48.6g (0.243mol) of C_12/14Mixing the fatty alcohol. 2% by weight of sulfuric acid (50%) was added as a catalyst. Introducing N into a stirring vessel equipped with a means for azeotropic removal of water₂Next, the reaction mixture was heated at 150 ℃ for 7 hours. Subsequently, 4.03g (0.024mol) of phthalic acid were added and heating was continued at 180 ℃ for 2 hours. The hydroxyl number of the product obtained was 658mg KOH/g.

Preparation of copolymer III

In a stirred vessel equipped with a reflux condenser and dropping funnel, 215g of copolymer II (1mol) were heated at 70 ℃. Is reduced by a dropping funnel to 2A total of 196g of H were added₃PO₄(50%). After the end of the dropwise addition, the reaction mixture was stirred at 100 ℃ for a further 8 hours.

The following example shows the bioactive effect of polyglyceryl ethers compared to polyglyceryl esters on the herbicide glyphosate.

Determining foliar uptake of glyphosate added to the copolymer

¹⁴C-Glyphosate test

With 0.25% of the copolymer and a concentration of 20mM (aq) (equivalent to 665g ae/ha in spray volume 2001/ha)¹⁴Mixing C-glyphosate-IPA. Using this mixture, the foliar absorption of solanum (Solanumnigrum L.) was determined by means of scintillation (szITILLIationsmessung). The effect of the copolymer on the absorption of the active ingredient by the blade surface (lobe absorption) is described in the following table:

table 1: effect of copolymers I-V on Glyphosate weeding (Solanum nigrum):

auxiliary agent	Uptake (% of glyphosate applied)
		Is free of	48
Copolymer I	63
		Copolymer II	50
Copolymer III	68
		Copolymer IV	56
Copolymer V	59

In the presence of the crosslinked polyglyceryl ethers used in the present invention, the foliar absorption of the active ingredient (glyphosate) can be significantly increased compared to polyglyceryl esters.

Preparation of copolymer IV (PG ester, no crosslinking)

In a stirred vessel equipped with a means for azeotropic removal of water and passing N₂Next, 180g of polyglycerin n ═ 9.7(0.243mol) and 24.70g of coconut fatty acid (0.212mol) were added. Subsequently, the reaction mixture was heated and stirred at 220 ℃ for 7 hours.

Preparation of copolymer V (PG ester, crosslinked)

In a unit equipped with azeotropic removal of water and passing N₂180g of polyglycerin n ═ 9.7(0.243mol) and 24.70g of coconut fatty acid (0.212mol) in a stirred vessel of (a)) And 10.13g of phthalic acid (0.061 mol). Subsequently, the reaction mixture was heated at 220 ℃ for 7 hours with stirring.

Bentazone test

The bentazone sodium salt is applied as an aqueous solution with a concentration of 480 g/l. The application rate was 60 gai/ha. The mixture was applied to Chenopodium (CHEAL) and wild Fagopyrum (POLCO) plants. The adjuvant was added to the application solution at a concentration of 0.25%. Activity determination by fluorescence, where factor F_pcThe photosynthesis is measured. The destruction of the plants is accompanied by F_pcThe value drops, initially 100, to 0.

Table 2: 1 DAT (DAT: days after treatment), Effect of copolymers I-III on the herbicidal Activity of bentazone sodium salt (CHEAL, POLCO) at 60g/ha

Auxiliary agent	Fluorescence FCHEAL	Fluorescence FPOLCO
			Is free of	56	46
Copolymer I	21	33
			Copolymer II	18	17
Copolymer III	10	12
			Untreated	75	72

Nicosulfuron (nicosulofon) test

Nicosulfuron was applied as an aqueous solution at a concentration of 200 gai/ha. The adjuvant was added to the application solution at a concentration of 0.25%. The mixture is applied to Abutilon (ABUTH), Chenopodium (CHEAL) and Stellaria (STEME) plants. The effect was determined 14 days after application (14 DAT) by weighing the plants (fresh weight g).

Table 3: 14 DAT (DAT: days after treatment), the Effect of the copolymers I to III on the herbicidal Activity of nicosulfuron (ABUTH, CHEAL, STEME) on FW (g) (fresh weight)

Auxiliary agent	ABUTH	CHEAL	STEME
				Is free of	90	88	63
Copolymer I	43	18	20
				Copolymer II	45	18	21
Copolymer III	62	38	43
				Untreated	100	100	100

Claims (5)

1. An agricultural composition comprising

A) Glyphosate

B) A copolymer having a hydroxyl number of 658-1000mg KOH/g was prepared from

a) Polyglyceryl ethers

b) One or more dicarboxylic acids and/or polycarboxylic acids,

the polyglyceryl ethers are as defined in formula (I)

Wherein the radical R¹、R²And R³Each of which is the same or different and represents hydrogen, optionally 1 to 3 (C)₁-C₄) -alkyl substituted (C)₁-C₃₀) -alkyl, optionally via 1 to 3 (C)₁-C₄) -alkyl substituted (C)₂-C₃₀) -an alkenyl group;

n represents a number from 4 to 10;

and the designations p1, q1, r1, p2, q2, r2, p3, q3 and r3 represent numerical values of 0;

provided that

The compound of formula (I) contains a free OH group, and R¹、R²And R³At least one of (a) represents (C)₁-C₃₀) -an alkyl group.

2. An agricultural composition according to claim 1, the group R in formula (I)¹、R²And R³Each of which is the same or different and represents hydrogen, optionally 1 to 3 (C)₁-C₄) -alkyl substituted (C)₁-C₃₀) -an alkyl group.

3. An agricultural composition according to claim 1 wherein n in formula (I) represents 5 to 10.

4. The agricultural composition according to any one of claims 1 to 3, the di-and/or polycarboxylic acid being phthalic acid, isophthalic acid and/or terephthalic acid.

5. The agricultural composition of claim 4 wherein the dicarboxylic acid and/or polycarboxylic acid is phthalic acid.