EP3758482A1 - Compositions à base de siloxanes cycliques utilisées en tant qu'agents mouillants à diffusion étendue et lente pour la protection phytosanitaire - Google Patents

Compositions à base de siloxanes cycliques utilisées en tant qu'agents mouillants à diffusion étendue et lente pour la protection phytosanitaire

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Publication number
EP3758482A1
EP3758482A1 EP19706274.8A EP19706274A EP3758482A1 EP 3758482 A1 EP3758482 A1 EP 3758482A1 EP 19706274 A EP19706274 A EP 19706274A EP 3758482 A1 EP3758482 A1 EP 3758482A1
Authority
EP
European Patent Office
Prior art keywords
formula
cyclic siloxanes
integer
polyether
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19706274.8A
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German (de)
English (en)
Inventor
René HÄNSEL
Alissa SINGER
Katja SKRABANIA
Michael Ferenz
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Evonik Operations GmbH
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Evonik Operations GmbH
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Filing date
Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP3758482A1 publication Critical patent/EP3758482A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants

Definitions

  • compositions based on cyclic siloxanes as slow superspreiter for crop protection
  • the present invention relates to special compositions comprising cyclic siloxanes, processes for their preparation, their use as adjuvants in plant protection and as tank mix additive in spray liquors.
  • adjuvants In crop protection, so-called “adjuvants”, also referred to as “additives” or “adjuvants”, are used to improve the biological effectiveness (also referred to as effectiveness) of pesticides or pesticide mixtures.
  • PSD Pesticides Safety Directorate
  • HSE Health and Safety Executive
  • an adjuvant as a substance that works alongside water, not itself as a pesticide, but its effectiveness of a pesticide (http://www.hse.gov.uk/pesticides/topics/pesticide-approvals/pesticides- registration / applicant-guide / the-applicant-guide-adjuvan.htm).
  • the terms surfactant or wetting agents are occasionally used in patents or literature as a synonym, but they are far too far-reaching and can be interpreted as a generic term. Because of the use envisaged here, the term “adjuvant” is used as defined in Regulation (EC) No 1 107/2009 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 21 October 2009 concerning the placing of plant protection products on the market and repealing Directives 79/1 17 / EEC and 91/414 / EEC, Article 2 (3) (d).
  • Crop protection agents are often not water soluble. In order to spread the pesticides effectively on the plants, adjuvants for the aqueous spray liquor are indispensable to compensate for the poor wetting of surfaces by way of the physical influence of the aqueous solutions.
  • the crop protection active ingredients can be dispersed, for example, in aqueous solutions as fine particles, often with a particle diameter ⁇ 10 microns.
  • the dispersant But it can also be a plant-based oil, or an oil based on mineral oil fractions.
  • emulsifiers are added to the formulation.
  • the crop protection agents can also be added as a powder or granules of the spray mixture.
  • These powders or granules contain surface-active substances so that the solids can disperse in the water and then be sprayed onto the plants as a spray mixture. Furthermore, there are pesticides that are completely dissolved in a liquid.
  • the spray mixture can only work optimally if the spray drops adhere to the plants and spread on the plants. It helps to reduce the surface tension of the spray mixture. Low surface tensions cause the spray drop to adhere to the sheet and not peel off. The jumping off of the spray drops arises because plants have very hydrophobic surfaces, which leads to the repulsion of water. If the surface tension of water or of the spray mixture is lowered, the drops adhere to the blade, at the same time the contact angle to the surface is lowered and better wetting is achieved. The lower the surface tension, the lower the contact angle of the spray drop to the surface and the better the wetting.
  • Adjuvants also help overcome technical application issues such as low water usage, different water qualities and the trend of increased application speeds.
  • the enhancement of pesticidal efficacy, as well as the balancing of pesticide deficiencies of the pesticides, are generally referred to as increasing the effectiveness or enhancing the efficacy of the pesticide application.
  • Growth regulators to preserve plant products, provided that such substances or products are not subject to specific Community legislation on preservatives; (d) destroy unwanted plants or parts of plants, with the exception of algae, unless the products are spread on the ground or in water to protect plants; (e) inhibit or prevent undesirable growth of plants, with the exception of algae, unless the products are applied to soil or water to protect plants.
  • the pesticides used in crop protection are also referred to as pesticides.
  • the pesticides may be, for example, herbicides, fungicides, insecticides, growth regulators, molluscicides, bactericides, viridicides and micronutrients.
  • Pesticide mixtures can also be used.
  • the spray mixture may contain one or more pesticides.
  • the pesticides are used in the permitted quantities which can be found on the label of the packaging. The amount of water and concentration of the spray mixture is also given by the pesticide manufacturer.
  • Pesticidal agents are associated with their uses, e.g. listed in The Pesticide Manual, 14th edition, 2006, The British Crop Protection Council. Pesticide is always used as a collective term.
  • the plant protection products are diluted in water by the user, and sprayed on the plants by means of a nozzle, the spray drops should spread well on the plant, in order to ensure an optimal effect.
  • the pesticides are usually added to a tank of water as the content and distributed with stirring in the so-called spray mixture to dilute the concentrated formulation of the active ingredient before spraying and make the plants compatible.
  • Adjuvants are either formulated into the crop protection formulation before tank mixing or added to the broth as separate tank mix additives.
  • Adjuvants are usually added to the aqueous spray mixture shortly before application and spraying as a tank mix additive or incorporated directly into crop protection formulations.
  • the adjuvants are usually added in concentrations of 0.001% by volume to 1% by volume of the spray mixture.
  • adjuvants synthetic surfactants such as e.g. ethoxylated alcohols, Nonylphenolethoxylate or alkyl polyglycosides used.
  • synthetic surfactants such as e.g. ethoxylated alcohols, Nonylphenolethoxylate or alkyl polyglycosides used.
  • water-soluble, hydrophilic polyglycerol esters as adjuvants in crop protection formulations is likewise known from the publications WO 2002/034051 and US 2006-0264330 A1. In general, these adjuvants have in common that they are water-soluble hydrophilic substances.
  • trisiloxane surfactants are often used as adjuvants. These trisiloxane surfactants reduce the static surface tension of spray liquors or water significantly more than pure organic surfactants.
  • Trisiloxane surfactants have the general structure Me3SiO-SiMeR-OSiMe3, where R is a polyether radical.
  • superspreading trisiloxane surfactants such as BREAK-THRU® S-240, Evonik Industries AG, in combination with a pesticide, results in an enhancement of pesticide uptake by the plant and, more generally, an increase in efficacy or effectiveness of the pesticide.
  • the static surface tension of trisiloxane surfactants is about 20 to 25 mN / m.
  • the extremely low surface tension ensures a very good wetting.
  • the superspreitende effect leads to a contact angle of 0 °. Since the droplet containing the plant protection product is thus distributed over a large area on the leaf, the distribution of the pesticide on the leaf also improves, which leads to an increase in the biological activity of the plant protection product.
  • a 50 ml drop of a solution of 0.1% by weight of the adjuvant in water after examination based on ASTM E2044-99 (2012), has a spreading diameter of at least 55 mm a standard polypropylene film (type: Forco-OPPB, Fa. Van Leer, a biaxially oriented polypropylene film) has.
  • a 50 ⁇ l drop of a solution of 0.1% by weight of the adjuvant in water on the standard polypropylene film spreads to an area of at least 25 cm 2 .
  • the spreading at 25 ° C is examined, preferably the spreading is determined at an atmospheric humidity of 50% and a pressure of 1013.25 mbar.
  • the lower surface tension of the spray mixture is responsible for the adhesion of the spray drop, the lower it is, the better the drop adheres to the plant.
  • the superspreitende effect is observed after the application of the drop.
  • the low surface tension in combination with the superspreitenden effect makes the trisiloxane surfactants worldwide preferred adjuvants.
  • WO 1994/02231 1, WO 2016/202564 and EP 3106033 A1 disclose superspreading compositions containing polyether-modified trisiloxanes.
  • Polyether-modified trisiloxanes as wetting agents are therefore known from the prior art.
  • the spread of trisiloxanes such as Silwet® L 77 or Silwet® 408 from Momentive or BREAK-THRU® S-240 from Evonik or Sylgard® 309 from Dow Corning is very fast.
  • the very fast spreading often leads to the run-off of the spread spray mixture from the plant.
  • dispersed particles can also be entrained outwards, which in turn leads to an uneven distribution, much like a coffee ring, on the plant. This uneven distribution leads to damage to the plant in some pesticides, since the pesticides are partially highly concentrated on the plant.
  • Cyclic polyether-modified siloxanes are also known from the prior art.
  • EP 2 099 81 1 A1 describes, for example, organomodified cyclic siloxanes whose organomodifying group is bonded to the silicon atom via an oxygen atom (SiOC linkage).
  • organomodifying groups polyether radicals are disclosed.
  • the cyclic siloxanes should be producible in an economical and technically simple way and have a pronounced interfacial activity. Mixtures of these cyclic siloxanes are described which should lead to an efficacy enhancement of crop protection agents. However, the mixtures only contain those cyclic siloxanes which have exactly one organomodifying group.
  • cyclic siloxanes with polyether radicals are known. These cyclic siloxanes are used to reduce the surface tension of aqueous compositions. These compositions can be selected from varnishes, printing inks, household cleaners, floor care products, pigment and filler pastes, crop protection agents and cosmetic care products.
  • cyclic siloxanes with polyether radicals can be selected from varnishes, printing inks, household cleaners, floor care products, pigment and filler pastes, crop protection agents and cosmetic care products.
  • the ratio of the molar amount of the cyclic tetrasiloxanes having exactly one polyether radical to the molar amount of the cyclic tetrasiloxanes having exactly two polyether radicals is more than 4.5.
  • the polyether-modified cyclic siloxanes of the prior art lead to smaller spreit vom compared to the polyether-modified trisiloxanes.
  • the superspreitende effect is therefore either not given or not very pronounced.
  • the object of the present invention was to overcome at least one disadvantage of the prior art.
  • compositions which have a comparable superspreitenden effect as the known polyether-modified trisiloxanes, but in addition have a lower spreading speed in order to reduce runoff of the spread spray mixture from the plant or an uneven distribution of the plant protection agent on the plant.
  • compositions comprising specific mixtures of cyclic siloxanes as described in the claims overcome at least one disadvantage of the prior art.
  • the compositions according to the invention of the cyclic polyether-modified siloxanes show a longer spreading time than polyether-modified trisiloxanes with a comparable polyether modification, the surface tension and the spreading diameter being comparable.
  • compositions comprising mixtures of cyclic tetrasiloxanes in which the mole ratio of cyclic tetrasiloxanes having just one polyether residue to cyclic tetrasiloxanes having exactly two polyether residues is less than 4.5 are both superspreading and slow-spreading.
  • compositions according to the invention are described below by way of example, without the invention being restricted to these exemplary embodiments.
  • ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If% information is given, this is, unless otherwise stated, by mole fractions. In the case of compositions, the percentages, unless stated otherwise, refer to the total composition. If averages are given below and in advance, unless otherwise indicated, they are weight average (weight average).
  • unsaturated describes the presence of one or more carbon-carbon triple bonds and / or carbon-carbon double bonds that are not part of an aromatic ring. Specific embodiments are defined below, so that features such as indexes or structural components can be constrained by execution. For all features that are not affected by the restriction, the remaining definitions remain valid.
  • a first subject of the present invention is a composition comprising cyclic siloxanes according to formula (I),
  • Each R 1 is independently a monovalent hydrocarbon radical having from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably a linear or branched, aliphatic or aromatic, optionally unsaturated, monovalent hydrocarbon radical, even more preferably methyl, ethyl, propyl or phenyl, especially preferably methyl;
  • R 2 is in each case independently of one another a monovalent polyether radical which is preferably bonded via an Si-C bond, more preferably a polyether radical of the formula
  • AO are each independently an alkylenyloxy radical selected from ethyleneoxy, propyleneoxy and / or butyleneoxy, even more preferably a polyether radical according to formula (III),
  • g is an integer from 2 to 30, preferably 3 to 20 , more preferably 4 to 15, still more preferably 4 to 12, particularly preferably 8 to 12;
  • h is an integer selected from 1, 2 or 3, preferably 1 or 2, particularly preferably 1;
  • o is an integer from 1 to 25, preferably 2 to 15, particularly preferably 3 to 10,
  • p is an integer from 0 to 20, preferably 0 to 10, particularly preferably 2 to 8,
  • R 3 is in each case independently of one another a polyvalent, preferably di- or trivalent hydrocarbon radical having 2 to 12 carbon atoms, preferably having 3 to 10 carbon atoms, optionally additionally containing 1 to 4 heteroatoms, preferably 1 to 4 oxygen atoms; more preferably R 3 is also linear or branched, aliphatic or aromatic, optionally unsaturated, even more preferably R 3 is selected from the group consisting of:
  • Each R 5 is independently hydrogen or a monovalent hydrocarbon radical of 1 to 18 carbon atoms, preferably linear or branched, aliphatic or aromatic, optionally unsaturated, more preferably methyl or phenyl; characterized in that: cyclic siloxanes D 1 3 D 2 i and D 1 2 D 2 2 according to formula (I) are included; and the ratio of the molar amount of the cyclic siloxanes D 1 3 D 2 i to the molar amount of cyclic siloxanes D 1 2 D 2 2 less than 4.5, preferably from 0.2 to 4.3, more preferably from 0.5 to 4, 0, even more preferably from 1, 0 to 3.5, even more preferably from 1, 5 to 3.5, particularly preferably from 2.5 to 3.5.
  • a first subject of the present invention is therefore a composition comprising cyclic siloxanes according to formula (I),
  • b is an integer from 0 to a
  • Each R 1 is independently a monovalent hydrocarbon radical having 1 to 12 carbon atoms
  • Each R 2 is independently a monovalent polyether radical; characterized in that: cyclic siloxanes D 1 3 D 2 i and D 1 2 D 2 2 according to formula (I) are included; and the ratio of the molar amount of the cyclic siloxanes D 1 3 D 2 i to the molar amount of the cyclic siloxanes D 1 2 D 2 2 is less than 4.5.
  • cyclic siloxanes according to formula (I) may be present:
  • the composition preferably comprises cyclic siloxanes of the formula (I) in which R 1 is selected from methyl, ethyl, propyl or phenyl; in which, furthermore, R 2 is a polyether radical of the formula (II); in which furthermore R 3 represents the radical -CH 2 CH 2 CH 2 -; and wherein also R 4 is selected from hydrogen, methyl or acetyl.
  • Each R 1 is independently methyl, ethyl, propyl or phenyl;
  • Each R 2 is independently a polyether radical of formula (II);
  • R 3 is -CH 2 CH 2 CH 2 -;
  • Each R 4 is independently hydrogen, methyl or acetyl.
  • Each R 1 is independently methyl, ethyl, propyl or phenyl;
  • R 2 is in each case independently of one another a polyether radical of the formula (II)
  • AO are each independently an alkylenyloxy radical selected from ethyleneoxy, propyleneoxy and / or butyleneoxy, where:
  • g is an integer of 2 to 30, preferably 3 to 20, more preferably 4 to 15, even more preferably 4 to 12, particularly preferably 8 to 12;
  • h is an integer selected from 1, 2 or 3, preferably 1 or 2, particularly preferably 1;
  • R 3 is -CH 2 CH 2 CH 2 -;
  • Each R 4 is independently hydrogen, methyl or acetyl.
  • R 1 is more preferably methyl and / or R 4 is hydrogen.
  • the composition comprises cyclic siloxanes of the formula (I) in which R 1 is methyl; and wherein also R 2 is a polyether radical of formula (III); and wherein further R 3 represents the radical -CH 2 CH 2 CH 2 -; and where R 4 is also hydrogen.
  • R 1 is methyl
  • Each R 2 is independently a polyether radical of formula (III);
  • R 3 is -CH 2 CH 2 CH 2 -;
  • R 4 is hydrogen
  • R 1 is methyl
  • R 2 is in each case independently of one another a polyether radical of the formula (III) -R 3 [0 [CH 2 CH 2 O] o [CH 2 CH 2 (CH 3) 0] P R 4 ] h Formula (III);
  • g is an integer of 2 to 30, preferably 3 to 20, more preferably 4 to 15, even more preferably 4 to 12, particularly preferably 8 to 12;
  • R 3 is -CH 2 CH 2 CH 2 -;
  • Each R 4 is independently hydrogen, methyl or acetyl.
  • R 2 is in each case independently of one another a polyether radical of the formula (III), where the following applies:
  • g is an integer from 4 to 15;
  • h 1;
  • o is an integer of 3 to 10;
  • p is an integer from 2 to 8.
  • R 2 is in each case independently of one another a polyether radical of the formula (III)
  • h 1;
  • o is an integer of 3 to 10;
  • p is an integer from 2 to 8.
  • o + p is an integer from 4 to 15.
  • R 2 is in each case independently of one another a polyether radical of the formula (III), where the following applies:
  • g is an integer from 8 to 12;
  • h 1;
  • o is an integer of 5 to 9;
  • p is an integer from 2 to 4.
  • R 2 is in each case independently of one another a polyether radical of the formula (III)
  • h 1;
  • o is an integer of 5 to 9;
  • p is an integer from 2 to 4.
  • o + p is an integer from 8 to 12.
  • R 2 is in each case independently of one another a polyether radical of the formula (III), where the following applies:
  • g is an integer from 8 to 12;
  • h 1;
  • o is an integer of 6 to 8;
  • p is an integer from 2 to 4.
  • R 2 is in each case independently of one another a polyether radical of the formula (III)
  • h 1;
  • o is an integer of 6 to 8;
  • p is an integer from 2 to 4.
  • o + p is an integer from 8 to 12.
  • cyclic siloxanes according to formula (I) with b equal to 1 and b equal to 2 may be present.
  • the ratio of the molar amount of all cyclic siloxanes according to formula (I) with b equal to 1 taken together to the molar amount of all cyclic siloxanes according to formula (I) with b equal to 2 is preferably less than 4.0, preferably 0.5 to 3.5 preferably from 1.0 to 3.0, particularly preferably from 1.5 to 2.5.
  • the cyclic siloxanes D 1 4 D 2 i and D 1 3 D 2 2 may be contained according to formula (I).
  • the ratio of the molar amount of the cyclic siloxanes D 1 4 D 2 i to the molar amount of cyclic siloxanes D 1 3 D 2 2 is less than 4.0, preferably 0.5 to 3.5, more preferably from 1, 0 to 3, 0, more preferably from 1, 5 to 2.5.
  • the sum of the mole fraction of the cyclic siloxanes according to formula (I) with b is 1 and b is 2 in the composition, based on the total amount of the cyclic siloxanes according to formula (I), at least 30%, preferably at least 40% , more preferably at least 50%, even more preferably at least 60%, even more preferably at least 70%, still further preferably at least 80%, more preferably at least 90%, even more preferably at least 99%, particularly preferably from 99.9 to 100%, wherein the maximum value is 100%.
  • the proportion of such cyclic siloxanes of the formula (I) which have one or two polyether radicals R 2 is particularly high.
  • the molar fraction of all cyclic siloxanes according to formula (I) with b taken together equal to 0, based on the total amount of cyclic siloxanes according to formula (I), is preferably less than 50%, more preferably less than 40%, even more preferably less than 30% , even more preferably less than 20%, even more preferably less than 10%, even more preferably less than 1%, and is more preferably from 0 to 0.1%, wherein the maximum value is 100%. Because it is advantageous if the mole fraction of cyclic siloxanes of the formula (I) having polyether radicals R 2 , is greater than the mole fraction of cyclic siloxanes having no polyether R 2 . Thus, there are advantageously less cyclic siloxanes which are not polyether-modified than those which are polyether-modified.
  • the cyclic siloxanes of the formula (I) which have no polyether radicals R 2 include, for example, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
  • Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane can accumulate in organisms.
  • Octamethylcyclotetrasiloxane is also toxicologically questionable.
  • the mole fraction of decamethylcyclopentasiloxane based on the total amount of cyclic siloxanes according to formula (I) is less than 5%, more preferably less than 4%, even more preferably less than 3%, even more preferably less than 2% more preferably less than 1% and is more preferably from 0 to 0.1%, wherein the maximum value is 100%.
  • the mole fraction of octamethylcyclotetrasiloxane based on the total amount of cyclic siloxanes according to formula (I) is less than 5%, more preferably less than 4%, even more preferably less than 3%, even more preferably less than 2%, even more preferably less than 1%, particularly preferably from 0 to 0.1%, wherein the maximum value is 100%.
  • the compositions of the invention have no further polyether-modified siloxanes except those of formula (I). It is further preferred that the mole fraction of the polyether-modified cyclic tetrasiloxanes based on the total amount of cyclic siloxanes according to formula (I) at least 5%, preferably at least 10%, more preferably at least 20%, even more preferably at least 30%, even more preferred at least 40%, even more preferably at least 50%, even more preferably at least 60%, even more preferably at least 70%, even more preferably at least 80%, even more preferably at least 90%, wherein the maximum value is 100%.
  • the sum of the mole fraction of all cyclic siloxanes according to formula (I) with a is 4 and b is 1 to 4 based on the total amount of cyclic siloxanes according to formula (I) at least 5%, preferably at least 10% preferably at least 20%, more preferably at least 30%, even more preferably at least 40%, even more preferably at least 50%, even more preferably at least 60%, even more preferably at least 70%, even more preferably at least 80%, most preferably at least 90%, the maximum value being 100%.
  • the molar fraction of the polyether-modified cyclic pentasiloxanes based on the total amount of cyclic siloxanes according to formula (I) is from 5% to 45%, preferably from 10% to 40%, more preferably from 15% to 30%, where the maximum value is 100%. It is thus preferred that the sum of the mole fraction of all cyclic siloxanes of the formula (I) with a is 5 and b is 1 to 5, based on the total amount of cyclic siloxanes according to formula (I) of 5% to 45%, preferably 10 % to 40%, more preferably from 15% to 30%, the maximum value being 100%.
  • the mole fraction of the polyether-modified cyclic hexasiloxanes based on the total amount of cyclic siloxanes according to formula (I) is from 0% to 10%, preferably from 0% to 5%, the maximum value being 100%. It is thus preferred that the sum of the mole fraction of all cyclic siloxanes of formula (I) with a is 6 and b is 1 to 6 based on the total amount of cyclic siloxanes according to formula (I) from 0% to 10%, preferably from 0 % to 5%, with a maximum value of 100%.
  • the polyether radical of the formula (III) has the ethyleneoxy and propyleneoxy units in certain ratios. It is therefore preferred that the quotient o / p of the indices o and p is from 0.2 to 3.6, preferably from 0.6 to 3.2, more preferably from 1, 0 to 2.8, even more preferably from 1.4 to 2.4, more preferably from 1.9 to 2.8.
  • compositions therefore comprise cyclic siloxanes according to formula (I) with:
  • R 1 methyl
  • R 2 -CH 2 CH 2 CH 2 O [CH 2 CH 2 O ] O [CH 2 CH (CH 3) O ] P H;
  • o is an integer of 3 to 10, preferably 5 to 9, especially 6 to 8;
  • p is an integer of 2 to 8, preferably 2 to 4, especially 2 to 4; with the proviso that:
  • o + p 4 to 15, preferably 8 to 12, especially 8 to 12;
  • o / p 0.2 to 3.6, preferably 1.4 to 2.8, in particular 1.9 to 2.1.
  • Preferred polyether radicals R 2 are, for example:
  • compositions of the invention are that they have superspreading properties in water as defined above.
  • the area of a drop on a polypropylene film is determined as described in more detail in the examples.
  • the mixture of the cyclic siloxanes of the formula (I) with water in a mass ratio of 1: 999 preferably has a spreading area of from 25 to 70 cm 2 , preferably from 30 to 60 cm 2 , more preferably from 35 to 50 cm 2 . Even more preferably, the compositions according to the invention on the aforementioned Spreit Chemistry at a temperature of 25 ° C, a pressure of 1013.25 mbar and 50% relative humidity determined on.
  • the mixture of the cyclic siloxanes of the formula (I) with water in a mass ratio of 1: 999 has a spreading diameter of 5 to 10 cm, preferably 6 to 9 cm, particularly preferably 7 to 8 cm. More preferably, the compositions of the invention have the aforementioned spreading diameter at a temperature of 25 ° C, a pressure of 1013.25 mbar and 50% relative humidity determined on.
  • compositions according to the invention are slow spreading in water, ie that the time required for the maximum spreading is comparatively high.
  • the time required for the maximum spread is preferably not too high either.
  • the mixture of the cyclic siloxanes of the formula (I) with water in a mass ratio of 1: 999 preferably has a spreading time of from 90 to 280 s, preferably from 100 to 260 s, more preferably from 120 to 240 s, even more preferably from 140 to 220 s, more preferably from 160 to 200 s.
  • the compositions according to the invention on the aforementioned spreading time at a temperature of 25 ° C, a pressure of 1013.25 mbar and 50% relative humidity determined on.
  • compositions of the invention are their biodegradability.
  • the biodegradability is preferably determined according to the OECD 301 F method. More preferably, the biodegradability is determined according to OECD 301 F after 28 days at 22 ° C. Most preferably, the biodegradability is determined as described in the Examples.
  • the mixture of the cyclic siloxanes of the formula (I) has a biodegradability of greater than or equal to 60%, preferably greater than or equal to 63% and particularly preferably greater than or equal to 65%, the maximum value being 100% ,
  • compositions of the invention do not contain siloxanes which are not biodegradable.
  • composition according to the invention is that cyclic siloxanes are contained as a mixture, and thus an expensive fractional distillation can be dispensed with.
  • the composition according to the invention is technically readily available and inexpensive to produce.
  • a further subject matter of the present invention is a process for preparing a composition according to the invention, comprising at least one process step in which a composition comprising cyclic siloxanes of the formula (IV)
  • AO are each independently an alkylenyloxy radical selected from ethyleneoxy, propyleneoxy, and / or butyleneoxy, even more preferably with a polyether of the formula (VI),
  • R 4 is as defined for formula (II) and (III);
  • Each R 6 is independently a mono- or polyvalent, preferably a mono- or dihydric, unsaturated, preferably terminally unsaturated hydrocarbon radical having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms, optionally additionally containing 1 to 4 heteroatoms, preferably 1 to 4 oxygen atoms ; more preferably R 6 is also linear or branched, aliphatic or aromatic but in each case unsaturated, even more preferably R 6 is selected from the group consisting of:
  • cyclic siloxanes D 1 3 D 3 i and D 1 2 D 3 2 according to formula (IV) are included; and the ratio of the molar amount of cyclic siloxanes D 1 3 D 3 i to the molar amount of cyclic siloxanes D 1 2 D 3 2 less than 4.5, preferably from 0.5 to 4.0, more preferably from 1, 0 to 3, 5, more preferably from 1, 5 to 3.5, particularly preferably from 2.5 to 3.5.
  • Another object of the present invention is thus a process for preparing a composition according to the invention, comprising at least one process step, in which a composition comprising cyclic siloxanes of the formula (IV)
  • cyclic siloxanes according to formula (IV) with b equal to 1 and b equal to 2 may be present.
  • the ratio of the molar amount of all cyclic siloxanes according to formula (IV) with b equal to 1 taken together to the molar amount of all cyclic siloxanes according to formula (IV) with b equal to 2 is preferably less than 4.0, preferably 0.5 to 3.5 preferably from 1.0 to 3.0, particularly preferably from 1.5 to 2.5.
  • the cyclic siloxanes D 1 4 D 3 i and D 1 3 D 3 2 may be contained according to formula (IV).
  • the ratio of the molar amount of the cyclic siloxanes D 1 4 D 3 i to the molar amount of the cyclic siloxanes D 1 3 D 3 2 is less than 4.0, preferably 0.5 to 3.5, more preferably from 1, 0 to 3, 0, more preferably from 1, 5 to 2.5.
  • the sum of the mole fraction of the cyclic siloxanes according to formula (IV) with b is 1 and b is 2 in the composition, based on the total amount of the cyclic siloxanes according to formula (IV), at least 30%, preferably at least 40% , more preferably at least 50%, even more preferably at least 60%, even more preferably at least 70%, even more preferably at least 80%, even more preferably at least 90%, wherein the maximum value is 100%.
  • the proportion of such cyclic siloxanes of the formula (IV) which have one or two SiH groups is particularly high, which in turn makes the proportion of those cyclic siloxanes which carry one or two polyether radicals particularly high in the process product.
  • the molar fraction of all cyclic siloxanes of formula (IV) taken together with b equal to 0, based on the total amount of cyclic siloxanes according to formula (IV), is preferably less than 50%, more preferably less than 40%, even more preferably less than 30% , even more preferably less than 20%, and is more preferably from 0 to 10%, wherein the maximum value is 100%. Because it is advantageous if the mole fraction of cyclic siloxanes of the formula (IV) having SiH groups is greater than the mole fraction of cyclic siloxanes which have no SiH groups. Thus, there are advantageously less cyclic siloxanes which have no SiH groups than those which have SiH groups. Thus, advantageously in the process product are less cyclic siloxanes which are not polyether-modified than those which are polyether-modified.
  • the mole fraction of SiH-functional cyclic tetrasiloxanes based on the total amount of cyclic siloxanes according to formula (IV) at least 5%, preferably at least 10%, more preferably at least 20%, even more preferably at least 30%, even further preferably at least 40%, even more preferably at least 50%, even more preferably at least 60%, even more preferably at least 70%, even more preferably at least 80%, even more preferably at least 90%, the maximum value being 100%.
  • the sum of the mole fraction of all cyclic siloxanes of the formula (IV) with a is 4 and b is 1 to 4 based on the total amount of cyclic siloxanes according to formula (IV) at least 5%, preferably at least 10% preferably at least 20%, more preferably at least 30%, even more preferably at least 40%, even more preferably at least 50%, even more preferably at least 60%, even more preferably at least 70%, even more preferably at least 80%, most preferably at least 90%, the maximum value being 100%.
  • the mole fraction of the SiH-functional cyclic pentasiloxanes based on the total amount of cyclic siloxanes according to formula (IV) is from 5% to 45%, preferably from 10% to 40%, more preferably from 15% to 30%, where the maximum value is 100%. It is thus preferred that the sum of the mole fraction of all cyclic siloxanes according to formula (IV) with a is 5 and b is 1 to 5 based on the total amount of cyclic siloxanes according to formula (IV) of 5% to 45%, preferably of 10 % to 40%, more preferably from 15% to 30%, the maximum value being 100%.
  • the mole fraction of the SiH-functional cyclic hexasiloxanes based on the total amount of cyclic siloxanes according to formula (IV) is from 0% to 10%, preferably from 0% to 5%, the maximum value being 100%. It is therefore preferred that the sum of the mole fraction of all cyclic siloxanes of the formula (IV) with a is 6 and b is 1 to 6, based on the total amount of cyclic siloxanes according to formula (IV) from 0% to 10%, preferably from 0 % to 5%, with a maximum value of 100%.
  • the polyether of the formula (VI) has the ethyleneoxy and propyleneoxy units in certain ratios. It is therefore preferred that the quotient o / p of the indices o and p is from 0.2 to 3.6, preferably from 0.6 to 3.2, more preferably from 1, 0 to 2.8, even more preferably from 1.4 to 2.4, more preferably from 1.9 to 2.8.
  • g is an integer from 4 to 15;
  • h 1;
  • o is an integer of 3 to 10;
  • p is an integer from 2 to 8. It is even more preferred for the polyether according to formula (VI):
  • g is an integer from 8 to 12;
  • h 1;
  • o is an integer of 5 to 9;
  • p is an integer from 2 to 4.
  • g is an integer from 8 to 12;
  • h 1;
  • o is an integer of 6 to 8;
  • p is an integer from 2 to 4.
  • the polyether-modified cyclic siloxanes of the formula (I) are prepared by hydrosilylation in the manner known to the person skilled in the art.
  • the corresponding SiH-functional cyclic siloxanes according to formula (IV) are reacted with unsaturated polyethers by known processes.
  • the hydrosilylation reaction of the process according to the invention is preferably catalyzed with the aid of the platinum group catalysts familiar to the person skilled in the art, more preferably with the aid of Karstedt catalysts.
  • the hydrosilylation reaction of the process according to the invention is preferably brought to a complete conversion in relation to the hydrogen content of the SiH-functional siloxane of the formula (IV).
  • Complete conversion in the context of the present disclosure is understood to mean that the conversion of SiH functions is> 99%.
  • the detection is carried out in the manner known to those skilled in the art, preferably gas volumetric after alkaline decomposition. In this case, for example, a sample of the reaction mixture with a butanolic Natriumbutanolat solution (sodium butoxide content: 5 wt .-%) reacted and concluded on the basis of the amount of hydrogen formed on the remaining amount of SiH functions.
  • the process product according to the invention is preferably purified in a further process step, preferably by means of a thermal separation process.
  • Thermal separation processes are known to those skilled in the art and include all processes based on the adjustment of a thermodynamic phase equilibrium.
  • Preferred thermal separation processes are selected from the list containing distillation, rectification, adsorption, Crystallization, extraction, absorption, drying and freezing, particularly preferred are methods of distillation and rectification.
  • the proportion of volatile constituents is reduced at a pressure of less than 100 mbar, more preferably less than 10 mbar, and a temperature of from 100 ° C. to 150 ° C., preferably from 110 ° C. to 140 ° C. for example at 1 mbar and 130 ° C.
  • the majority of the volatile constituents are at a pressure of less than 100 mbar, more preferably less than 10 mbar, and a temperature of 100 ° C to 150 ° C, preferably from 1 10 ° C to 140 ° C. is removed, for example at 1 mbar and 130 ° C.
  • the volatile constituents are, for example, cyclic siloxanes of the formula (I) which have no polyether radicals, ie those cyclic siloxanes of the formula (I) where b is 0.
  • cyclic siloxanes octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
  • the volatile constituents do not include the cyclic siloxanes of the formula (I) which have polyether radicals, ie those cyclic siloxanes according to formula (I) with b not equal to 0. Cyclic siloxanes according to formula (I) with b of 1 to a represent in the sense The present invention thus provides no volatiles.
  • the mole fraction of all cyclic siloxanes according to formula (I) can be taken together with b not equal to 0, based on the total amount of cyclic siloxanes according to formula (I), to more than 50% preferably more than 60%, even more preferably more than 70%, even more preferably more than 80%, even more preferably more than 90%, even more preferably more than 99%, in particular preferably 99.9 to 100%, where the maximum value is 100%.
  • the molar ratios of the non-volatile ingredients such as the cyclic siloxanes of the formula (I) having polyether groups do not change in the composition.
  • the ratios of the molar proportions of the cyclic siloxanes according to formula (I) with b not equal to 0 thus remain unchanged.
  • the polyethers of the formula (V) and (VI) and also the polyether radicals of the formula (II) and (III) can be of random construction. Statistical distributions are block by block with any number of blocks and any sequence or subject to a randomized distribution, they can also be constructed alternately or form a gradient over the chain, in particular they can also form all mixed forms, where appropriate, groups of different distributions can follow one another. Incidentally, the propyleneoxy units in formulas (V) and (VI) and formulas (II) and (III) may be different from the adjacent groups or atoms.
  • [CH 2 CH (CH 3) O] each independently represents a propyleneoxy group of the form [CH 2 CH (CH 3) O] and / or the form [CH (CH 3) CH 2 O ], but preferably for a propyleneoxy of the form [CH 2 CH (CH 3) 0].
  • Special designs may cause statistical distributions to be constrained by execution. For all areas that are not affected by the restriction, the statistical distribution does not change.
  • the cyclic siloxanes of the formula (I) and (IV) can be of random construction.
  • Statistical distributions are block-by-block with any number of blocks and any sequence or subject to a randomized distribution, they can also be of alternating construction, in particular they can also form all hybrid forms, in which groups of different distributions may possibly follow one another. Special designs may cause statistical distributions to be constrained by execution. For all areas that are not affected by the restriction, the statistical distribution does not change.
  • the products of the process according to the invention preferably have no further polyether-modified siloxanes which do not correspond to the products of the process according to the invention.
  • compositions according to the invention can be prepared by the methods of the prior art, but preferably by the method according to the invention.
  • cyclic polyethersiloxanes The synthesis of cyclic polyethersiloxanes is familiar to the person skilled in the art and described, for example, in DE19631227. There is described both the synthesis of isolated cyclic polyether siloxanes starting from isolated cyclic SiH-functional siloxanes, including the synthesis of mixtures of cyclic polyether siloxanes starting from mixtures of cyclic SiH-functional siloxanes.
  • the cyclic SiH-functional siloxanes can also be obtained by known methods by equilibration / cyclization and distillation as described in US3714213, US4895967 or US5247116. In this way mixtures of cyclic SiH-functional siloxanes can be prepared. By distillation, the cyclic SiH-functional siloxanes can also be separated from one another, ie isolate, and reused as a single compound. The cyclic SiH-functional siloxanes, which are separated, for example, by fractional distillation, can in turn be used to produce mixtures of different compositions. From these mixtures, the compositions according to the invention can be prepared by means of hydrosilylation reaction.
  • compositions according to the invention can also be prepared from their individual compounds, ie from individual, isolated polyether-modified siloxanes. This can be done, for example, by mixing cyclic siloxanes of the formula (I).
  • the cyclic siloxanes according to formula (I) can be prepared from the corresponding, for example by fractional distillation isolated SiH-functional siloxanes via a hydrosilylation.
  • the inventive method has the advantage that SiH-functional siloxanes according to formula (IV) can be used as a mixture, and that can be dispensed with a complicated fractional distillation.
  • Another object of the present invention is the use of the compositions of the invention and / or the novel process products in crop protection.
  • compositions according to the invention Preference is given to the use of the compositions according to the invention and / or of the process products according to the invention as adjuvants in crop protection.
  • the adjuvant according to the invention is suitable with all pesticides for all plants.
  • the adjuvant is used together with herbicides, fungicides, insecticides, growth regulators and macro and micronutrients (fertilizers), preferably with herbicides.
  • compositions according to the invention may comprise one or more further components.
  • the component is at least one crop protection agent.
  • These other components may be selected from herbicides, fungicides, insecticides, growth regulators and fertilizers, preferably herbicides.
  • Preferred fertilizers are macro and micronutrients.
  • compositions according to the invention and / or the process products according to the invention are preferably used as tank mix additive for spray liquors.
  • the mass fraction of all cyclic siloxanes according to formula (I) based on the total mass of the spray mixture from 0.001% to 1%, more preferably from 0.01% to 0.5%.
  • preferred use concentrations are between 0.001 and 1% by volume, preferably between 0.01 and 0.5% by volume and more preferably between 0.02 and 0.1% by volume (correspondingly also 0.1% by weight) .- %) of the spray mixture. This is equivalent to 10 to 3000 ml / ha, when usually 100 to 1000 I spray mixture per ha are applied, and preferably corresponds to an adjuvant amount of 50 to 700 ml / ha, which are also added by the respective Spritzbrühmengen regardless of the total amount of water per ha ,
  • Active substances are those substances which have been authorized and / or registered and / or listed in the individual countries for use on plants and crops in order to protect plants against damage or for the loss of yield by pests or the like in a crop or to eliminate unwanted by-products, such as weeds and / or grass weeds, or to provide the plant with nutrients (also called fertilizers). They are commonly referred to as pesticides or pesticides. In general, active ingredients are incorporated into formulations for handling and efficiency.
  • crop protection formulations are usually diluted with water via nozzles and, in addition to the active component, also contain other auxiliaries, such as emulsifiers, dispersing aids, anti-freeze agents, defoamers, biocides and surface-active substances, such as surfactants.
  • Active substances in particular fungicides, insecticides and nutrients, may also be applied to seed (seed) of plants alone or in combination and provided with other auxiliaries as indicated above by various methods. Such methods are also called seed treatment methods. Seed treatment with fungicides and insecticides can protect plants from disease and insect infestation at an early stage of growth.
  • the increased spreading time of the compositions according to the invention and / or the process products according to the invention leads, in particular, to an increase in the biological activity in comparison, ie an increase in the activity of the crop protection agent, which is attributable to the lower effluent (often also referred to as "run off") of the spray drops Plant can be justified. There remains more pesticide on the plant. Furthermore, the slower spreading leads to a more homogeneous distribution on the plant. These effects lead to better biological effectiveness and safer use. Examples
  • the spreading was examined by applying a 50 ⁇ l drop of the test solutions to a standard horizontal polypropylene film (type: Forco-OPPB, Van Leer, biaxially oriented polypropylene film). The drop was applied with a micropipette. The maximum spread area (spreading area) and the time required to reach the maximum expansion of the drop (spreading time) were determined after application.
  • the Spreitungs malmesser is the diameter of the approximately circular area.
  • the surface tension was determined using the Wilhelmy plate method with a Kruss K 12 tensiometer.
  • the mass fraction of the SiH-functional cyclic siloxanes can be determined in the context of the present invention by a gas chromatographic method (GC method) in which the substances are separated according to the boiling point and detected by means of a thermal conductivity detector. An aliquot of the sample to be analyzed is analyzed by GC without further dilution. This is carried out in a gas chromatograph equipped with a split / splitless injector, a capillary column and a thermal conductivity detector under the following conditions:
  • Carrier gas helium, const. flow 2 mL / min
  • the SiH-functional cyclic siloxanes are separated according to their boiling point.
  • the mass fraction of the individual substances is determined as a percentage of the peak areas determined for the respective substance in comparison to the total area of all detected substances (area% method).
  • the polyether-modified siloxanes were prepared by hydrosilylation. SiH-functional siloxanes were reacted with an unsaturated polyether. The hydrosilylation reaction was carried out in the presence of a platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complete solution in xylene (purchased from Sigma-Aldrich, Pt content: 2% by weight) as Karstedt catalyst performed.
  • a platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complete solution in xylene purchased from Sigma-Aldrich, Pt content: 2% by weight
  • Hydrosilylation reaction was brought to a complete conversion in terms of the hydrogen content of the SiH-functional siloxanes.
  • complete conversion means that more than 99% of the SiH functions have been reacted.
  • the detection is carried out in a manner known to those skilled gasvolumetrisch after alkaline decomposition.
  • Example 1 (according to the invention):
  • R 2 -CH 2 CH 2 CH 2 O [C 2 H 4 O] 6 [CH 2 CH (CH 3) O] 3H
  • R 2 -CH 2 CH 2 CH 2 O [C 2 H 4 O] 6 [CH 2 CH (CH 3) O] 3H
  • the ratio of the molar amount of the cyclic siloxanes D 1 3 D 2 i to the molar amount of the cyclic siloxanes D 1 2 D 2 2 is 6.4.
  • Solutions or emulsions of Examples 1 to 6 in distilled water were prepared.
  • the concentration of the test solutions was 0.1% by weight of the particular example based on the total weight of the solution or emulsion.
  • Example 1 according to the invention leads to a significantly higher spreading time than the examples 3 to 6 based on polyether-modified trisiloxanes.
  • the physicochemical properties of Inventive Example 1 and Examples 3 to 6 are comparable in terms of surface tension and spreading diameter.
  • Example 2 which is not according to the invention and which is based on cyclic polyether-modified siloxanes shows a very high spreading time, but the spreading diameter is markedly reduced compared to the other examples.
  • Example 2 an evaporation of the aqueous film is observed at the outer edges, with the result that the spread film is no longer uniformly homogeneous and has holes.
  • Example 1 shows both a high spreading time and a large spreading diameter.
  • compositions of the invention glasshouse experiments were carried out in combination with a fungicide.
  • the influence of adjuvants on the effect of sulfur against mildew on barley was investigated.
  • a so-called leaf segment test was performed.
  • Six barley plants per pot were sown in Fruhsdorfer soil (special mixture "fine") and grown in the greenhouse for three weeks.
  • As a variety "Golden Promise” was chosen because it is known for its high susceptibility to mildew.
  • a mixture of water, sulfur and, if appropriate, adjuvant as spray mixture was applied to the plants according to the test protocol (see Table 4), the spray quantity of the spray mixture corresponding to the water contained being 200 l / ha.
  • composition according to the invention achieved a marked improvement in activity compared with a polyether-modified trisiloxane.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des compositions spéciales renfermant des siloxanes cycliques, des procédés de production correspondants, leur utilisation en protection phytosanitaire et en tant qu'additifs de mélange de réservoir dans des mélanges à pulvériser.
EP19706274.8A 2018-02-26 2019-02-21 Compositions à base de siloxanes cycliques utilisées en tant qu'agents mouillants à diffusion étendue et lente pour la protection phytosanitaire Withdrawn EP3758482A1 (fr)

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EP18158534 2018-02-26
EP18168183 2018-04-19
PCT/EP2019/054278 WO2019162360A1 (fr) 2018-02-26 2019-02-21 Compositions à base de siloxanes cycliques utilisées en tant qu'agents mouillants à diffusion étendue et lente pour la protection phytosanitaire

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Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3714213A (en) 1971-01-06 1973-01-30 Gen Electric Method of making cyclopolysiloxanes containing silanic hydrogen
US4895967A (en) 1988-09-26 1990-01-23 General Electric Company Method for making cyclic poly(siloxane)s
US5247116A (en) 1992-07-10 1993-09-21 Temple University Of The Commonwealth System Of Higher Education Acid-catalyzed process for the production of cyclosiloxanes
DE69413165T2 (de) 1993-03-30 1999-01-28 Osi Specialties Inc Stark spreitendes schaumarmes tensid für landwirtschaftliche spraymischungen
DE19631227C1 (de) 1996-08-02 1998-04-23 Byk Chemie Gmbh Cyclische Siloxane und deren Verwendung als Benetzungshilfsmittel und Schaumstabilisatoren
DE10052588A1 (de) 2000-10-24 2002-05-02 Cognis Deutschland Gmbh Pestizidhaltige wäßrige Mittel
DE10307171B4 (de) 2003-02-20 2009-04-16 Clariant Produkte (Deutschland) Gmbh Copolymere enthaltende landwirschaftliche Mittel
DE102006060115A1 (de) * 2006-12-20 2008-06-26 Evonik Goldschmidt Gmbh Cyclische Siloxane und deren Verwendung
PL3106033T3 (pl) 2015-06-16 2017-09-29 Evonik Degussa Gmbh Biodegradowalny super rozprzestrzeniający się organomodyfikowany trisiloksan

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