HK1065220B - Pesticidal preparations comprising copolymers - Google Patents

Description

Pesticide formulations comprising copolymers

The invention relates to pesticide formulations comprising copolymers obtained by the copolymerization of glycerol, dicarboxylic acids and monocarboxylic acids. The action of the copolymer increases the biological activity of the pesticide (herbicide, insecticide, fungicide, bactericide, molluscicide, nematicide and rodenticide).

Plant protection agents are chemically synthesized or natural substances which penetrate into plant cells, plant tissues or parasites in or on plants, destroying and/or destroying them. The herbicide constitutes the largest proportion of pesticides, following the insecticides and fungicides.

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

The biological activity of the pesticide is determined by the active time and active concentration at which it acts, due to damage to the plant caused by influences of active ingredients on the leaves or growth of the plant involved.

For optimum pesticidal effect, the pesticide must either wet the chlorophyll and remain there for a sufficiently long time, or the penetration of the active substance from the leaf surface must be accomplished. The general problem here is that only a small part of the active substance achieves a satisfactory effect, for example, only a small part is applied to the harmful plants and weeds and can adhere there for a sufficiently long time to penetrate the plant cells. About the vast majority of the fluid is lost without effect.

To overcome this ecological and economic disadvantage, most pesticide liquors are supplemented with adjuvants which increase the wettability, solubility, emulsifiability or absorbability of the active substance, as described in most patent specifications. In addition, the adjuvants can facilitate and accelerate the penetration of the active substance from the leaf surface into the interior of the plant.

WO 98/06259 describes a method for assisting the biological activity of plant protection agents, according to which aqueous surfactants are used together with the active substance as a co-formulation or sprayed onto the plants after application of the active substance. The wetting agents used are aqueous silicones and/or organofluorine compounds. The oils of EP 379852 and US 4853026 are added to the herbicide N-phosphonomethylglycine (glyphosate) as a water-in-oil emulsion to improve contact between the hydrophilic active and the plant lipophilic epidermis. The emulsion has the disadvantage of being insufficiently stable.

According to WO 99/05914, the improvement of the effect of anionic pesticides can be achieved by preparing the anionic active substance with protonated polyamines or derivatives thereof as a hydrocolloid dispersion.

It is shown in US 5858921 that if a water-soluble long chain alkyl dimethyl amine oxide and a water-soluble quaternary ammonium halide are added to the formulation, the concentration of glyphosate can be reduced, but the biological activity is not reduced.

US 5750468 describes glyphosate formulations containing tertiary or quaternary ether amines (ether amines) as adjuvants.

All described methods for increasing the biological activity of pesticides have been successful to date only to a certain extent. It is therefore an object of the present invention to develop a novel pesticidal composition or formulation, in particular a herbicide of the N-phosphonomethylglycine (glyphosate) type, which has improved activity, at the same time as reasonable cost, ease of handling and good tolerance to humans and the environment. Glyphosate is a herbicide with good tolerance to the environment and high efficiency and wide application, and is widely used 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 else as a free acid in the form of a liquor or a solid formulation, and a wetting agent is applied to the plant leaves and weeds, acting on the transport system of the plants and destroying them.

We have surprisingly found that the pesticidal activity of the plant protection agents is significantly improved upon addition of a copolymer obtained by copolymerization of glycerol, a dicarboxylic acid and a monocarboxylic acid.

The cross-linking of the polyglycerol by means of the dicarboxylic acid produces a network-like concentrated product. Surprisingly, the crosslinked polyglycerols exhibit a significantly high efficiency as compared to the non-crosslinked polyglycerols. The effect can be influenced in a predetermined manner by the degree of crosslinking.

Crosslinking also contributes to the electrolytic stability of the formulation. In addition, the viscosity of the formulation can be adjusted in a predetermined manner depending on the degree of crosslinking.

The invention provides pesticide preparations comprising at least one copolymer obtained by copolymerization of

a) Glycerol

b) At least one dicarboxylic acid and

c) at least one monocarboxylic acid of the formula (I)

R¹-COOH (I)，

Wherein R is¹Is (C)₅-C₂₉) An alkyl group; (C)₇-C₂₉) An alkenyl group; phenyl or naphthyl.

Radical R¹The alkyl or alkenyl group in (1) may be linear or branched. The phenyl or naphthyl group may be substituted, the preferred substituent being (C)₁-C₆) Alkyl, (C)₁-C₆) Alkenyl, (C)₁-C₆) Alkoxy, -CHO, -CO ((C)₁-C₆) Alkyl) or halogen.

Preferred dicarboxylic acids b) are oxalic acid; dicarboxylic acids of the general formula (II)

HOOC-R²-COOH (II)

And/or dicarboxylic acids of the general formula (III),

wherein R is²Is (C)₁-C₄₀) Alkylene bridges, preferably (C)₁-C₁₀) Alkylene, particularly preferably (C)₁-C₄) Alkylene or is (C)₂-C₂₀) Alkenylene bridges, preferably (C)₂-C₆) Alkenylene, particularly preferably C₂-alkenylene, and

r is one or more groups selected from: 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) Alkyl groups). R in the general formula (II)²And may be linear or branched.

Dimeric fatty acids, such as Pripol acid, are also included in formula (II).

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

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

Very particularly preferred dicarboxylic acids b) are phthalic acids.

Preferred monocarboxylic acids c) are those in which R is¹Is (C)₇-C₂₂) Alkyl or (C)₇-C₂₂) Alkenyl monocarboxylic acids.

Particularly preferred monocarboxylic acids c) are saturated or unsaturated fatty acids or mixtures thereof, for example coconut acid (cocout acid), oleic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, linoleic acid, linolenic acid, palmitic acid and tallow fatty acid.

More particularly preferred monocarboxylic acids c) are coconut acids and tallow fatty acids.

Very particularly preferred monocarboxylic acids c) are coconut acid.

Particularly advantageous copolymers are those obtained by copolymerization of glycerol, phthalic acid and coconut acid.

Preferably, the copolymers contain from 19.9 to 99% by weight of structural units of component a), from 0.1 to 30% by weight of structural units of component b) and from 0.9 to 80% by weight of structural units of component c).

The copolymers particularly preferably contain from 50 to 90% by weight of structural units of component a), from 1 to 25% by weight of structural units of component b) and from 2 to 49% by weight of structural units of component c).

The content of structural units of component b) of from 1 to 10% by weight is particularly advantageous for the properties of the copolymers.

The preferred copolymers have an OH number of 400-1000mg KOH/g (determined in accordance with DIN 53240).

The viscosity of the 100% strength copolymer, measured at 60 ℃ with a rotary viscometer, is advantageously in the range from 1500 to 35000 mPas. Higher viscosities are also possible but hinder the handling of the material. The copolymer is preferably operated at a concentration of 75 to 90% by weight in the liquor.

The copolymer can be obtained by copolymerization of

a) Glycerol

b) At least one dicarboxylic acid and

c) at least one monocarboxylic acid of the general formula (I).

The copolymerization is preferably carried out by first polymerizing the glycerol component a) to give the polyglycerol and then copolymerizing the polyglycerol with a mixture of the dicarboxylic acid component b) and the monocarboxylic acid component c).

In a further preferred variant, the glycerol component a) is first polymerized to give a polyglycerol, and then the dicarboxylic acid component b) is copolymerized and then the monocarboxylic acid component c) is copolymerized.

In a likewise preferred variant, the glycerol component a) is first polymerized to give the polyglycerol, and then the monocarboxylic acid component c) is copolymerized and then the dicarboxylic acid component b) is copolymerized.

However, the copolymerization is not limited to the above-described modification.

For example, in a variant it is also advantageous to polymerize a portion of the glycerol a) to oligomers and then to copolymerize the dicarboxylic acid component b), the monocarboxylic acid component c) and the remainder of the glycerol a).

Preferred embodiments of the copolymerization are described by the following examples.

A) Polymerization of glycerol to oligo-or poly-glycerol:

the polymerization of glycerol into oligoglycerol or polyglycerol can be carried out as standard at 240 ℃ and 270 ℃ in a stirred apparatus with a water separator and nitrogen input. The catalyst used was a 50% strength sodium hydroxide solution in the concentration range from 0.1 to 0.4% by weight. After 5-20 hours, the polymerization is stopped, depending on the degree of polymerization desired. A sample was taken out to determine its OH value. The average molar mass of the oligoglycerol or the polyglycerol can be calculated from the OH number.

B) One-pot method of prepolymerized polyglycerol:

the polyglycerol was mixed in the molten state with the dicarboxylic acid and the monocarboxylic acid in the desired molar ratio in a stirred vessel with a water separator and heated at 200-240 ℃ for 7 hours with stirring. The acid value of the final product was less than 1mg KOH/g.

C) The polyglycerol is first copolymerized (crosslinked) with a dicarboxylic acid and then with a monocarboxylic acid:

the polyglycerol was mixed in the molten state with the dicarboxylic acid in the desired molar ratio in a stirred vessel with water trap and stirred with heating at 200-240 ℃ for 2 hours. The resulting product was clear and homogeneous. The monocarboxylic acid was then added and esterified at 200 ℃ and 240 ℃ for 5 hours. The acid value of the final product was less than 1mg KOH/g.

D) Polyglycerol was first copolymerized with monocarboxylic acids and then dicarboxylic acids (crosslinking):

the polyglycerol was mixed in the molten state with the monocarboxylic acid in the desired molar ratio in a stirred vessel with water trap and stirred under heating at 200 ℃ and 240 ℃ for 5 hours. The acid number of the product obtained was less than 1mg KOH/g. The dicarboxylic acid was then added in the desired molar ratio and esterified at 200-240 ℃ for 2 hours. The acid value of the final product was less than 1mg KOH/g.

The copolymers are suitable for addition as adjuvants to pesticide formulations for increasing the biological activity of herbicides, insecticides, fungicides, acaricides, bactericides, molluscicides, nematicides and rodenticides. The copolymers are preferably used in herbicide formulations.

Particularly suitable herbicides are glyphosate (N-phosphonomethylglycine) and salts and/or derivatives thereof. Examples of suitable water-soluble salts are alkali metal salts, ammonium salts, alkylamine salts, alkylsulfonium salts, alkylphosphonium salts, sulphonamide salts or aminoguanidine salts.

Examples of further suitable herbicides are acifluorfen, asulam, benazolin, bentazone, bialaphos, bromacil, bromoxynil, mefenpyr, clopyralid, 2, 4-D, 2, 4-DB, dalapon, dicamba, 2, 4-dichlorvonic acid, diclofop-methyl, fluazifop-p-butyl, imidazopyr, fluoroglycofen, fomesafen, fosfamid, glufosinate-ammonium, fluazifop-methyl, imazethapyr-methyl, imazamethabenz-ethyl, imazamox, imazapyr, imazaquin, imazethapyr-methyl, loxynil, MCPA, MCPB, 2-4-mefenac/MSMA, naproxen, picloram, quinclorac, quizalofop-ethyl, 2, 3, 6-TBA and TCA.

The pesticide formulation of the present invention may include almost any concentration of the copolymer.

Particularly preferred formulations are "tank-mix formulations" 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 here is preferably from 1: 10 to 500: 1, particularly preferably from 1: 4 to 4: 1.

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

Alternatively, the formulations of the present invention may be prepared in solid form such as powder, pill, tablet or granule, and dissolved in water prior to use. The solid preparations 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 preparation may contain conventional thickeners, anticoagulants, antifreezes, solvents, dispersants, emulsifiers, preservatives, further auxiliaries, binders, antifoams, diluents, disintegrants and wetting agents.

Thickeners that may be used are xanthan gum and/or cellulose, for example, carboxy, methyl, ethyl, or propyl cellulose. The final composition preferably contains 0.01 to 5% by weight of a thickener.

Suitable solvents are 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 their esters, 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 their salts.

A suitable antifoam is polysilicon.

Other adjuvants that may be used are alcohol ethoxylates, alkyl polysaccharides, fatty amine ethoxylates, ethoxylate derivatives of sorbitan and sorbitol, and derivatives of alkyl (alkenyl) succinic anhydrides.

The mixing ratio of these auxiliaries to the copolymer is preferably in the range of 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, aluminium stearate, calcium or magnesium stearate, sodium tripolyphosphate, sodium tetraborate, sodium sulphate, silicates and sodium benzoate.

Suitable disintegrants are celluloses, such as carboxymethylcellulose, polyvinylpyrrolidone, sodium or potassium acetate, carbonates, bicarbonates, sesquicarbonates, ammonium sulfate or potassium bicarbonate.

Wetting agents that may be used are alcohol ethoxylates/propoxylates.

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

The preparation of the present invention can be used according to a conventional method.

The liquid and solid formulations are diluted with the corresponding amount of water before use. Preferably from 0.1 to 5kg, more preferably from 0.3 to 2.5kg of pesticide per hectare is used. The proportion of the copolymer is preferably from 0.1 to 3.0 kg/ha. The amount of the pesticide preparation to be applied by spraying is preferably 50 to 1000 l/ha.

The properties of the copolymers or of the pesticide formulations, for example water solubility, electrolytic stability, viscosity, affinity for the active ingredient of the plant protection agent, can be advantageously adjusted very easily by the degree of crosslinking. With regard to the degree of crosslinking, the nature and the content of the dicarboxylic acid component b) play a decisive role, the content being of particular importance.

It has surprisingly been found that highly concentrated solutions of anionic pesticides, particularly salts of glyphosate, and copolymers are phase stable. Even in the case of long-term storage, no crystallized ionic component was found.

In addition to high electrolytic stability, the use of the copolymers according to the invention also increases the affinity and contact of the hydrophilic active ingredient with the plant lipophilic epidermis.

The good wettability and absorbability of the pesticide preparation of the invention are beneficial to the exertion of the biological activity of the effective components on plants.

The present invention also provides a method for increasing the biological activity of a pesticide, comprising the use of a pesticide in the form of a pesticide formulation comprising a copolymer obtained by copolymerizing:

a) glycerol

b) At least one dicarboxylic acid and

c) at least one monocarboxylic acid of the general formula (I).

The process is preferably suitable for herbicides, in particular glyphosate and its salts and/or their derivatives.

Examples

The following examples are presented to demonstrate the effect of the copolymer on the biological activity of the herbicide glyphosate.

1) Preparation of copolymers I to V

Preparation of polyglycerol with n-9.7:

2000g of glycerol and 6.0g of NaOH (50%) were heated to 270 ℃ with stirring in a nitrogen feed and dehydrator with stirring. After a reaction time of 9 hours 444g of water were released and a sample was taken for the determination of the OH number. The OH number determined was 891mg KOH/g. This corresponds to an average degree of polymerization n of 9.7 glycerol units. The degree of polymerization can also be determined approximately by the viscosity or refractive index of the reaction mixture. For this purpose, a standard curve needs to be established in advance.

Preparation of copolymer I:

180.00g of a polyglycerol containing N9.7 (0.243mol) was added with N₂The mixture was transferred to a stirred vessel with a dehydrator and 24.70g of coconut fatty acid (C) was added₈/₁₈) (0.121mol) and 10.13g of phthalic acid (0.061 mol). The reaction mixture was then heated and stirred at 220 ℃ for 7 hours. The copolymer had an acid number of 0.40mg KOH/g.

Preparation of copolymer II:

190.00g of polyglycerol (0.256mol) with N being 9.7 added to N₂Transferred into a stirred vessel with a dehydrator and charged with 26.11g of coconut fatty acid (C)₈/₁₈) (0.128mol) and 4.32g of phthalic acid (0.026 mol). The reaction mixture was then heated and stirred at 220 ℃ for 7 hours. The copolymer had an acid number of 0.46mg KOH/g.

Preparation of copolymer III:

185.00g of polyglycerol (0.256mol) with N9.7 added to N₂The mixture was transferred into a stirred vessel with a water separator and crosslinked at 215 ℃ for 2 hours with 4.25g of phthalic acid (0.0256 mol). The reaction mixture was clear and homogeneous. Then 25.50g of coconut fatty acid (C)₈/₁₈) (0.125mol) was added to a stirred vessel and reacted at 215 ℃Should be 5 hours. The copolymer had an acid number of 0.38mg KOH/g.

Preparation of copolymer IV:

185.00g of polyglycerol (0.256mol) with N9.7 added to N₂The mixture was transferred into a stirred vessel with a water separator and crosslinked with 10.38g of phthalic acid (0.0625mol) at 215 ℃ for 2 hours. The reaction mixture was clear and homogeneous. 25.50g of coconut fatty acid (C)₈/₁₈) (0.125mol) was added to a stirred vessel and reacted at 215 ℃ for 5 hours. The copolymer had an acid number of 0.53mg KOH/g.

Preparation of copolymer V:

180.00g of a polyglycerol containing N9.7 (0.243mol) was added with N₂The mixture was transferred to a stirred vessel with a dehydrator and 24.75g of coconut fatty acid (C) was added₈/₁₈) (0.121mol) of esterification, 5 hours and an esterification temperature of 215 ℃ gave an acid number of 0.14mg KOH/g. 4.03g of phthalic acid were added and crosslinked at 215 ℃ for 2 hours. The final reaction product was clear and homogeneous.

Preparation of Experimental formulations containing copolymers I-V

The experimental formulations were prepared using in each case 200g, 300g and 500g of glyphosate and 600g of copolymer I-V and 300l of water, respectively. The weight data refer to 100% of active ingredient and 100% of adjuvant. The preparation corresponding to a ratio of 300l/ha was applied to the plant species Abutilon (ABUTH), Sesbania exaltata (SEBEX), Pharbitidis sativi (PHPHBHU), Galium aparine (GALAP), Amaranthus retroflexus (AMARE) and Echinochloa crusgalli (ECHCG) in the greenhouse and the growth of the plants was evaluated after 21 days at 20 ℃ according to the percentage measurement standard.

0% means no effect, 100% means complete destruction of the test plant. The effect of copolymers I-V on the herbicidal action of glyphosate is given in Table 1.

Table 1: effect of copolymers I-V on the herbicide Glyphosate

Glyphosate (g/ha)	Copolymer	SEBEX	AMARE	GALAP	ABUTH	ECHCG	PHBPU	Total of
									200300500	---	101530	204565	52040	01015	152040	102040	102238
200300500	III	758595	808590	255075	205575	708590	456585	537085
									200300500	IIIIII	355090	708595	457080	255070	658095	305580	456585
200300500	IIIIIIIII	406585	658085	356070	205065	607085	203555	406074
									200300500	IVIVIV	456595	708590	556570	305065	456590	305080	466382
200300500	VVV	355060	708595	254570	154065	507590	356595	386079

It is clear that the copolymer provides a significant improvement in the herbicidal action of glyphosate.

Claims (20)

1. A pesticide preparation comprising at least one copolymer obtained by copolymerization of

a) Glycerol

b) At least one dicarboxylic acid and

c) at least one monocarboxylic acid of the formula (I)

R¹-COOH (I)，

Wherein R is¹Is (C)₅-C₂₉) An alkyl group; (C)₇-C₂₉) An alkenyl group; phenyl or naphthyl, whichThe copolymer contains 19.9 to 99% by weight of component a), 0.1 to 30% by weight of component b) and 0.9 to 80% by weight of component c).

2. The pesticidal formulation of claim 1 wherein the dicarboxylic acid b) is oxalic acid; dicarboxylic acids of the general formula (II)

HOOC-R²-COOH (II)，

And/or dicarboxylic acids of the general formula (III),

wherein R is²Is (C)₁-C₄₀) Alkylene bridge or (C)₂-C₂₀) Alkenylene bridges and

r is selected from H, (C)₁-C₂₀) Alkyl, (C)₂-C₂₀) Alkenyl, phenyl, benzyl, halogen, -NO₂、(C₁-C₆) Alkoxy, -CHO or-CO ((C)₁-C₆) Alkyl) group.

3. The pesticide formulation as claimed in claim 2, wherein the dicarboxylic acid b) is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid and/or terephthalic acid.

4. The pesticide formulation as claimed in claim 3, wherein the dicarboxylic acid b) is phthalic acid, isophthalic acid and/or terephthalic acid.

5. The pesticidal formulation of claim 3, wherein the dicarboxylic acid b) is phthalic acid.

6. Pesticide formulation according to at least one of claims 1 to 5, wherein the monocarboxylic acid c) is a fatty acid or a mixture thereof.

7. The pesticide formulation as claimed in claim 6, wherein the monocarboxylic acid c) is coconut acid and/or animal fatty acid.

8. The pesticidal formulation of claim 6 wherein the monocarboxylic acid c) is coconut acid.

9. A pesticidal formulation as claimed in claims 4 and 7 wherein dicarboxylic acid b) is phthalic acid and monocarboxylic acid c) is coconut acid.

10. Pesticide formulation according to at least one of claims 1 to 9, wherein the copolymer contains 1 to 10% by weight of component b).

11. Pesticide formulation as claimed in at least one of claims 1 to 10, wherein the copolymer has an OH number of 400-1000mg KOH/g.

12. Pesticide formulation according to at least one of claims 1 to 11, wherein the viscosity of the copolymer at 60 ℃ is in the range of from 1500 to 35000 mPas.

13. Pesticidal formulations according to at least one of claims 1 to 12, wherein in the copolymerization process the glycerol component a) is first polymerized to give a polyglycerol which is then copolymerized with a mixture of dicarboxylic acid component b) and monocarboxylic acid component c).

14. Pesticidal formulations according to at least one of claims 1 to 12, wherein the glycerol component a) is first polymerized to give a polyglycerol, and then the dicarboxylic acid component b) is copolymerized and then the monocarboxylic acid component c) is copolymerized.

15. Pesticidal formulations according to at least one of claims 1 to 12, wherein the glycerol component a) is first polymerized to give a polyglycerol, and then the monocarboxylic acid component c) is copolymerized and then the dicarboxylic acid component b) is copolymerized.

16. The pesticide formulation as set forth in at least one of claims 1 to 12 wherein the pesticide is an herbicide, an insecticide, a fungicide, a bactericide, a molluscicide, a nematicide or a rodenticide.

17. The pesticide formulation of claim 16 wherein the pesticide is a herbicide.

18. The pesticide formulation as set forth in claim 17 wherein the herbicide is glyphosate, a salt thereof and/or a derivative thereof.

19. The pesticide formulation as set forth in at least one of claims 1 to 18 wherein the formulation is present in the form of: a "tank mix", "ready to use composition", concentrate, powder, pill, tablet or granule.

20. Method for increasing the biological activity of a pesticide, wherein at least one copolymer obtained by copolymerization of

a) Glycerol

b) At least one dicarboxylic acid and

c) at least one monocarboxylic acid of the formula (I)

R¹-COOH (I)，

Wherein R is¹Is (C)₅-C₂₉) An alkyl group; (C)₇-C₂₉) An alkenyl group; phenyl or naphthyl, wherein the copolymer contains 19.9 to 99% by weight of component a), 0.1 to 30% by weight of component b) and 0.9 to 80% by weight of component c).