DE10064406A1 - Stable aqueous herbicidal composition containing glyphosate and a cationic derivatized sugar to improve penetration and retention in plants and potentiate the herbicidal activity - Google Patents

Abstract

An aqueous composition (A) contains glyphosate (I) and a cationic derivatized sugar (II). An Independent claim is included for the use of (II) for potentiating the action of (I) in aqueous compositions.

Description

Field of the Invention

The invention is in the field of agrochemicals and relates to special aqueous agents, contain the pesticides in combination with additives that increase the pesticide effect.

State of the art

To protect valuable crops from pest infestation, water is often used in the landscape solutions or emulsions of pesticides. By choosing suitable additional Components (adjuvants), these formulations are adapted to the needs of practice. Because of the potential danger to the environment when using pesticides, there is a general problem may increase their effect through suitable application forms or through suitable formulation gladly. Furthermore, it is desirable that such agents even over long storage times at differ temperatures remain stable. Accordingly, an object of the present invention is therein pesticides with solid as well as liquid, water-soluble and oil-soluble pesticides to be made available, which is simultaneously characterized by a higher storage stability and activity (adjuvant effect) and in particular can be easily diluted with water. Farther and preferably the action of the pesticidal active ingredients should also be increased, so to reduce their use concentration. A well-known pesticide is glyphosate, for which already a variety of formulation proposals are known. For this, reference is made to WO 97/36493, proposes the aqueous glyphosate-containing agents to which polyethoxylated alcohols are used as adjuvants are given to improve the phytotoxicity of the active substance. From WO 00/38523 it is known Glyphosate in combination with betaines and possibly ethoxylated surfactants as "weather" to use so to increase the herbicidal effect. From DE 199 14 295 of the applicant it is known that katio nisch derivatized alkyl glucosides (APG) together with pesticides are stable emulsions train. However, a penetration-increasing effect is not described.

It has now been found that the combination of glyphosate with selected compounds from the The group of derivatized sugars also leads to a significant improvement in the pesticide effect and at the same time stable aqueous agents can be produced.  

Description of the invention

The invention relates to aqueous compositions containing at least

• a) glyphosate and
• b) cationically derivatized sugars

It has been found that agents containing glyphosate along with cationic derivatized sugars and if necessary, contain adjuvants that meet the requirements profile in an excellent manner. in the In particular, the derivatized sugars show improved penetration and retention of the glypho sats. The preparations are characterized by a compared to conventional emulsions of the stand the technology improved storage stability and higher activity. You can also easily with Dilute water and also allow the subsequent incorporation of other pesticides.

pesticides

The agents according to the invention contain glyphosate as an essential component. It is N- (phosphonomethyl) glycine, C ₃ H ₈ NO ₅ P, MW 169.07, melting point 200 ° C, LD ₅₀ (rat oral) 4320 mg / kg (WHO), a non-selective systemic leaf -Herbicide, which is preferably in the form of its isopropylamine salt for the total and semi-total control of weeds and weeds, including deep-rooted perennial species, on all arable crops, in fruit and. Viticulture is used. The structure is as follows:

In the context of the present applications, glyphosate includes all known to those skilled in the art Derivatives of glyphosate understood, so preferably its mono- or diethanolamine salts of Glyphosate. Sodium or potassium can also be used as cations. Is particularly preferred but the isopropylamine salt of glyphosate. Furthermore, any mixtures of these Ver bonds are used in the context of the inventive action.

The pesticides that continue to be considered as additional component (a) are preferably oil-soluble substances. There can be fungicides, herbicides, insecticides or their Mixtures are used. Typical examples of suitable fungicides are azoxystrobin, Benalaxyl, carbendazim, chlorothalonil, cupfer, cymoxanil, cyproconazole, diphenoconazole, dinocap, Epoxiconazole, fluazinam, flusilazole, flutriafol, Folpel, fosetyl aluminum, kresoxim methyl, hexacona zol, Mancozeb, Metalaxyl, Metconazol, Myclobutanil, Ofurace, Phentinhydroxid, Prochloraz, Pyremethanil,  Soufre, tebucanazole, and tetraconazole and mixtures thereof. Can be used as herbicides Alachlor, acloniphene, acetochlor, amidosulfuron, aminotriazole, atrazine, bentazone, biphenox, bromoxyl Octanoate, bromoxynil, clethodim, chlodinafop-propargyl, chloridazon, chlorsulfuron, chlortoluron, Clomazone, cycloxydim, desmedipham, dicamba, dicyclofop-methyl, diurea, difluphenicanil, di mithenamide, ethofumesate, fluazifop, fluazifop-p-butyl, fluorochloridone, fluroxypyr, glufosinate, glypho sat, Haloxyfop-R, Ioxynil Octanoate, Isoproturon, Isoxaben, Metamitron, Metazachlor, Metolachlor, Metsulfuron-Methyl, Nicosulfuron, Notflurazon, Oryzalin, Oxadiazon, Oxyfluorphen, Paraquat, Pendi methalin, phenmedipham, phenoxyprop-p-ethyl, propaquizafop, prosulfocarb, quizalofop, sulcotrione, Sulphosate, Terbutylazin, Triasulfuron, Trichlorpyr, Triflualin and Triflusulforon-Methyl individually or in Mixing can be used. Finally, biphenthrin, carbofuran, carbo come as insecticides sulfane, chlorpyriphos-methyl, chlorpyriphos-ethyl, β-cyfluthrin, λ-cyhalothrin, cyhexatin, cyper methrin, dicofol, endosulfan, τ-fluvalinate, α-methrin, δ-methrin, phenbutatin, pyrimicarb, terbuphos and Tebuphenpyrad and mixtures thereof. Other suitable pesticides can be found at for example the index Phytosanitaire 1998, 34th ed. (Ed .: Association de Coordination Technique Agricole, Paris).

Cationically modified sugar

As already indicated at the beginning, the cationic sugar derivatives (b) are known from those known per se Obtaining derivatization of sugar molecules. Sugar is used in the context of the present Applications generally understood monomeric, oligomeric or polymeric carbohydrates. Are there both the carbohydrates as such, and, preferably their reduced forms, and the alky gated and / or alkoxylated derivatives of such sugars suitable educts for the production of Cationic derivatives used according to the invention. These groups will also be reduced ten sugars, which are not further derivatized, used.

Particular preference is given to those sugars for the production of component (b) which are selected from compounds of the formula [G- (OR ") _n ] _k , in which G represents a cyclic or aliphatic sugar radical having 3 to 6 carbon atoms, n is a number between 3 and 6, R "is hydrogen or an alkyl radical having 1 to 22 C atoms or is a group (C ₂ H ₄ O) _m , and m is a number from 1 to 30, and k is a number from 1 to 150. Suitable sugars are, for example, fructose but also hexopyranoses idose, gulose, talose, altrose, allose, galactose, mannose, glucose and their reduced derivatives. Furthermore, the non-reduced sucrose can also be used for the production of components (b) according to the invention. In addition to the monomeric sugars, oligomeric or polymeric saccharides can also be used to produce the modified sugars used according to the invention. Here, the cyclodextrins but also the inulin, a polymeric fructose, are mentioned as examples.

The preparation is preferably carried out by reacting the hydroxyl groups of the above-mentioned glycosides with halogen compounds or epoxides which have a quaternary ammonium group. Such compounds follow the formula (I)

X-R'-NR ₃ ⁺ X ^- (I)
In the formula (I), R 'represents a divalent alkyl radical having 2 to 8 carbon atoms, it also being possible for the radical to be branched and / or functionalized. X represents a halogen atom, preferably chlorine. Before preferably R 'is a group -C ₃ H ₆ - or C ₃ H ₅ OH-. In the latter case the hydroxyl group is connected to the middle carbon atom of the chain. The radicals R independently of one another represent alkyl radicals having 1 to 24 carbon atoms. Those compounds of the formula (I) in which at least one radical R is an alkyl radical having 8 to 18 carbon atoms are particularly preferred. Compounds of the formula (I) in which one radical R is an alkyl radical having 8 to 18 carbon atoms and the other two radicals R are alkyl radicals having less than 8 carbon atoms, preferably an alkyl radical having 1 to 4, are particularly preferred C atoms and very particularly preferably a methyl radical.

Typical examples of suitable halogen compounds are 3-chloro- and 3-bromo-2-hydroxypropyl trialky-ammonium chlorides, which are sold by Degussa AG under the name "Quab®". The reaction between sugar and halogen compound takes place in the presence of strong bases as in for example sodium hydroxide, potassium hydroxide, sodium methylate or potassium tert-butoxide, which both in solid form as well as a concentrated aqueous solution can be used. The implementation typically takes place at milder temperatures of 30 to 50 ° C and reaction times of 12 to 68 Hours. The reactants sugar and halogen compound are usually approximated equimolar amounts or in excess Quab used, with the help of a base a pH is set in the range from 8 to 11.

Cationically derivatized sugars (b) are preferably based in the agents according to the invention used by polyfructoses. Inulin should be mentioned here in particular. The inulin is a linear polyfructosan with approx. 10 to 60 fructose units which are bound together by means of β2-1 binding who are linked. The number of fructose monomers in the polymer is indicated by the DP. This is preferably in the range from 10 to 30, in particular from 10 to 25. The molar mass of the The polymer itself is in the range from 500 to 5000, preferably in the range from 1000 to 2500 and in particular in the range from 1500 to 2000. The inulin is prepared with the compounds of the formula (I) preferably in molar ratios of 1: 1 to 1:10, in particular from 1: 2 to 1: 8, implemented. Be molar ratios between inulin and the compounds of formula (I) of 1: 2 are also preferred to 1: 4. The molar data for inulin in the context of the present application refers to the respective monomer unit for the arithmetic from the DP and the total molecular weight of the molecule  Average is formed. So here is a ratio of Quab to the respective monomer building blocks.

The preferred compound of the formula (I) is 3-chloro-2-hydroxypropyl-N, N-dimethyl-N-dodecyl chloride, which is commercially available under the name Quab® 342. In addition to inulin, others can According to the invention, polyfructoses are used to produce component (b), in particular being here called the Levan and its derivatives. For details on the manufacture and chemistry of this compound The publication "Carbohydrates as Organic Raw Materials", editor F. W. Lichtent haler, VCH Weinheim, 1991, pages 169 to 181.

adjuvants

In a preferred embodiment of the invention, in addition to the cationic sugar derivatives (b), the agents can also contain adjuvants (c) as optional components. For example, non-ionic surfactants from at least one of the following groups are suitable:

• 1. Addition products of 2 to 120 moles of ethylene oxide and / or 0 to 75 moles of propylene oxide linear fatty alcohols with 8 to 22 carbon atoms, fatty amines, on fatty acids with 8 to 22 carbon atoms Alkylphenols with 8 to 15 carbon atoms in the alkyl group and fatty amines with 6 to 22 carbon fatomen;
• 2. C _12/18 fatty acid _mono- , di and triesters of adducts of 1 to 120 moles of ethylene oxide with glycerol or technical oligoglycerols;
• 3. Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated Fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products;
• 4. Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxy analogs;
• 5. Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
• 6. Polyol and especially polyglycerol esters such as. B. polyglycerol polyricinoleate or polyglyce rinpoly 12-hydroxystearate. Mixtures of compounds of several are also suitable of these substance classes;
• 7. Addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;
• 8. _{partial esters} based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. Methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
• 9. trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;
• 10. wool wax alcohols;
• 11. Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;  
• 12. Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 11 65 574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methylglucose and polyo len, preferably glycerin,
• 13. Polyalkylene glycols as well
• 14 glycerol.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters as well as sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are homologous mixtures of which average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 20 24 051 as refatting agents for cosmetic preparations. C _8/18 alkyl mono- and oligoglycosides, their preparation and their use as surface-active substances are, for example, from US 3,839,318, US 3,707,535, US 3,547,828, DE-OS 19 43 689, DE-OS 20 36 472 and DE-A1 30 01 064 and EP-A1 0077167 known. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue applies that both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol, as well as oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

solvent

Especially when pesticides are to be incorporated into the emulsions, which are solids at room temperature, it is advisable to use non-polar solvents. As a further fa cultivative component (d) come, for example, mineral oils, alkyl aromatics and hydrocarbons such as z. B. are sold under the name Solvesso® by the Exxon company, Fettäu reniedrigalkylester, such as. B. the C ₁ -C ₄ -, ie the methyl, ethyl, propyl and / or butyl ester of Ca pronic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid; Myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Vegetable triglycerides such as coconut oil, palm oil, palm kernel oil, sunflower oil, olive oil and the like are also suitable. Polyethylene glycol is also a suitable solvent, preferably with molecular weights in the range from 90 to 600 and preferably from 120 to 250.

In a preferred embodiment, the agents according to the invention contain

• a) 0.01 to 60, preferably 0.5 to 55% by weight of pesticides,
• b) 0.05 to 45, preferably 1 to 30% by weight of cationically derivatized sugars
• c) 0 to 10, preferably 1 to 3 wt .-% adjuvants and
• d) 0 to 40, preferably 5 to 30% by weight of solvent,

with the proviso that the quantities indicated with water and possibly other usual Add auxiliaries and additives to 100% by weight. The water content of the funds is average 10 to 90 and in particular 30 to 60% by weight. The application solution for actual use contains component (a) in amounts of 0.01 to 5% by weight, preferably 0.1 to 2.5% by weight and in particular 0.1 to 1.5% by weight. Component (b) is contained in the application solution in Men gene from 0.05 to 5, preferably 0.5 to 3 and in particular from 0.5 to 2.0 wt .-% - all information based on the entire aqueous application solution.

However, the agents according to the invention can also be used as concentrates, for example with 10 to 90% by weight (a), 10 to 90% by weight (b) and 0 to 10% by weight (c) and 0 to 40% by weight (d) are distributed, respectively the actual use concentration is only set by dilution before use. The Water content in such concentrates is between 1 and 30% by weight.

Another object of the invention is directed to the use of the cationically derivatized Sugar (b) as an aid in aqueous pesticide formulations containing glyphosate, in which they are found in Men gen from 0.05 to 45, preferably 1 to 30 wt .-% - based on the agent - may be included. It was observed that the combination of glyphosate with the cationically modified sugars (b) surprisingly, the effect of the pesticides increases. In particular, here is a better penetration the active ingredients (a) can be observed in the plant surface. However, this makes it possible to concentrate Pesticide (a) and thus reduce the negative effects of the use of such pesticides Effectively reduce pesticides on the environment. Furthermore, the retention of the pesticide improves the leaf surface. An additional subject of the present application is therefore to Ver Use of cationically modified sugars (b) aimed at enhancing the action of glyphosate. A final subject relates to a method for controlling unwanted plant growth, wherein aqueous agents are applied to the undesirable plants as described above become. Typically, application quantities of 50 to 600 g glyphosate (active substance), preferably 100 to 350 g per hectare. The application takes place after all, the subject known methods, but especially by spraying.  

Examples Manufacture of cationically derivatized sugars Approach C cationically derivatized inulin in molar ratio * inulin: Quab® 342 1: 2 approach

• 1. 64 g 50% sodium hydroxide solution
• 2. 30 g dist. water
• 3. 65 g inulin Raftiline ST (DP 11, total molecular weight 1800)
• 4,684 g Quab 342 40% (Degussa)
• 5. approx. 26 ml 37% hydrochloric acid

* The molar ratio is calculated here as follows:
Quab (MW 342) = 684 / 342.0.4 = 0.8 mol.
Inulin (MW 1800, DP = 11 ⇒ average molecular weight per fructose unit) 1800/11 = 164, 65/164 = 0.4 mol.

execution

1 was introduced and then 3 was added and dissolved and stirred at 80.degree. Then the Add 2 within 0.5 h at 60 ° C. The mixture was then added by adding 5. neutralized and dialyzed in a dialysis tube MWCO 1000. The dialysis residue was frozen dried. Yield: 148 g.

Approach D cationically derivatized inulin in molar ratio inulin: Quab® 342 1: 4

Approach and test execution as above, but inulin Raftiline ST (DP 23) and Quab 342 implemented here in a molar ratio of 1: 4. Yield: 160 g.

Approach A cationically derivatized inulin in molar ratio inulin: Quab® 342 1: 1

Approach and experiment as above, but inulin and Quab 342 were here in the molver Ratio 1: 1 implemented.

Approach B cationically derivatized inulin in molar ratio inulin: Quab® 342 1: 1.5

Approach and experiment as above, but inulin and Quab 342 were here in the molver Ratio 1: 1.5 implemented.  

Application test

The effect of the agents according to the invention was determined by measuring the chloropyll fluorescence from Stellaria media (chickweed). The measurements were determined using a Pulse-Amplitude-Modulation Fluorometer (PAM) Model 2000, from Walz Effeltrich, DE. For this purpose, aqueous test solutions containing glyphosate and the compounds (b) according to the invention in amounts of 0.1% by weight were applied to the leaves by hand sprayer and their maximum fluorescence (Fm) was measured over a period of 240 h. the results can be found in FIG. 1. For comparison, glyphosate without sugar, as well as a commercially available glyphosate preparation (Roundup from Monsanto) and a blank sample (control) were measured. The surfactants added are listed in Table 1.

It can be seen that the combination of glyphosate according to the invention with cationically modified Sugar (b) sometimes shows better values than the Roundup.

Table 1

Claims (15)

1. Aqueous compositions containing at least

• a) glyphosate and
• b) cationically derivatized sugars

2. Composition according to claim 1, characterized in that component (b) is obtained by sugar with compounds of formula (I)
X-R'-NR ₃ ⁺ X ^- (I)
implemented, in this formula R 'represents a divalent alkyl radical having 2 to 8 C atoms, the radical may also be branched or functionalized, and the radicals R independently of one another represent alkyl radicals having 1 to 24 C atoms and X represents is a halogen atom. 3. Composition according to claim 2, characterized in that at least one of the radicals R in formula (I) represents an alkyl radical having 8 to 18 carbon atoms. 4. Composition according to claim 1 to 3, characterized in that the sugars of component (b) are selected from compounds of the formula [G- (OR ") _n ] _k , in which G represents a cyclic or aliphatic sugar residue having 3 to 6 C atoms, n is a number between 3 and 6, R "is hydrogen or an alkyl radical having 1 to 18 C atoms or for a group (C ₃ H ₆ O) m and / or (C ₂ H ₄ O ) _m is and m is a number from 1 to 30, and k is a number from 1 to 150. 5. Composition according to claim 1 to 4, characterized in that the sugar for the preparation of the Component (b) are selected from reduced sugars. 6. Composition according to claim 1 to 5, characterized in that the sugar for the preparation of the Component (b) are selected from polyfructoses. 7. Composition according to claim 1 to 6, characterized in that as a sugar for the production of Component (b) inulin is selected. 8. Composition according to claim 1 to 7, characterized in that component (b) is produced by reacting inulin with 3-chloro-2-hydroxypropyl-N, N-dimethyl-N-dodecyl chloride.   9. Agent according to at least one of claims 1 to 8, characterized in that it further contain adjuvants as optional component (c). 10. Composition according to claim 9, characterized in that they contain as component (c) adjuvants which are selected from the group formed by addition products of 2 to 120 moles of ethylene oxide and / or 0 to 75 moles of propylene oxide with linear fatty alcohols 8 to 22 carbon atoms, on fatty acids with 8 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group; Fatty amines with 6 to 22 carbon atoms C _12/18 fatty acid _mono- , di-, triesters of addition products of 1 to 120 mol ethylene oxide onto glycerol or oligoglycerols; Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products; Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; polyol esters; Addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil; Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols; alkyl glucosides; Trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates; Wool wax alcohols; Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives; Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols; Polyalkylene glycols and glycerine carbonate. 11. Agent according to at least one of claims 1 to 10, characterized in that it further contain as optional component (d) solvents. 12. Composition according to claim 1 to 11, characterized in that they are mineral oil as component (d), Contain alkyl aromatics, fatty acid lower alkyl esters and / or vegetable triglycerides. 13. Composition according to claim 1 to 12, characterized in that it

• a) 0.01 to 60 wt .-% pesticides
• b) 0.05 to 45% by weight of cationically derivatized sugars,
• c) 0 to 10 wt .-% nonionic co-emulsifiers and
• d) 0 to 40 wt .-% solvent

with the proviso that the amounts given with water and, if appropriate, other conventional auxiliaries and additives are 100% by weight. 14. Use of cationically derivatized sugars (b) according to claim 1 as an effect enhancer in aqueous, glyphosate-containing agents. 15. A method for combating undesirable plant growth, characterized in that a aqueous agent according to claim 1 is applied to the plants.