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
  • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
  • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

Definitions

• the present invention provides for the use of polyether-modified siloxanes as dust binder for seed, methods of reducing the evolution of dust from seed using polyether-modified siloxanes, treated seed obtainable by this use or by these methods, and seed-dressing compositions or seed-dressing liquors containing polyether-modified siloxanes.
• Seed is dressed prior to sowing.
• Seed is understood to mean dry, dormant, generative propagation organs such as seeds, fruits, accessory fruits, infructescences or parts thereof. These contain the germs of the plants.
• Dressing or seed dressing in agriculture and forestry and in landscaping and gardening is understood to mean the treatment of seed with crop protection products and optionally additionally nutrients in order to protect the seed from fungal degradation and from pests.
• the seed After the dressing, the seed has been ensheathed with a solid, dry and very substantially homogeneous layer. This sheath is usually coloured to indicate that the seed has been treated. The colouring is intended to prevent the accidental use of the dressed seed as animal feed or for food purposes.
• the formulations used for dressing are referred to as dressings, seed-dressing liquors or else as seed dressings.
• Seed dressings typically contain fungicides and/or insecticides as active crop protection ingredients. These active crop protection ingredients may be chemical or else biological in origin.
• Biological active crop protection ingredients used are typically specific fungal spores, bacteria or viruses.
• the active crop protection ingredients are usually used in the form of specific formulations. These are typically aqueous formulations in which the active crop protection ingredient is in concentrated form, also referred to hereinafter as seed-dressing composition or seed treatment composition.
• the usually water-insoluble active crop protection ingredients are dispersed here in the water with the aid of additives. This type of formulation is also called suspension concentrate.
• the active crop protection ingredient is dispersed in the form of small solid particles in water as dispersant (dispersing agent).
• Other seed formulations again are produced as emulsifiable concentrate.
• the organic crop protection products are dissolved here in an organic solvent that may contain emulsifiers and further additives.
• the commercial seed dressings based on aqueous suspension concentrates are generally more environmentally friendly than those based on emulsifiable concentrates.
• the seed-dressing compositions may likewise be formulated as oil dispersions, microemulsions or suspoemulsions, but these formulation types are less commonly used in seed dressings,
• the seed-dressing composition may contain further additives as well as crop protection agents and the additives mentioned, for example emulsifiers, dispersants, dyes or colour pigments. These additives include, for example, stickers. These stickers are intended to assure the adhesion of the crop protection material on the seed.
• the seed-dressing liquor is produced by diluting the seed-dressing composition in water. It takes the form of a dilute aqueous dispersion or emulsion.
• a customary seed-dressing liquor consists, for example, of:
• the seed-dressing liquor thus produced is applied to the seed with seed-dressing systems.
• the seed-dressing liquor is mixed with the seed in a continuous or batchwise process in the mixing drum (seed-dressing drum) of the seed-dressing system.
• the seed-dressing liquor is sprayed here by means of an impeller plate in the mixing drum containing the seed.
• the dosage is typically undertaken with a peristaltic pump; the end of the hose is typically just above the impeller plate.
• the procedure is typically such that the seed is introduced into the mixing drum, then the impeller plate is started and the seed-dressing liquor is finally sprayed in.
• the seed-dressing operation has typically ended after about 30 seconds.
• a very major problem in the sowing of the treated seed is the evolution of dust.
• the dust results from the abrasion of the crop protection formulation from the treated seed.
• the crop protection formulation can be rubbed off at the early stage of bagging of the dressed seed.
• the dust with its crop protection constituents can be distributed in the environment by wind. This is undesirable.
• the evolution of dust should be avoided as far as possible in order to avoid uncontrolled spread of the active crop protection ingredients present.
• the insecticides present in the seed-dressing products can harm beneficial insects, such as bees and bumblebees, and the fungicides present can be harmful to other plants.
• a dust binder antioxidant
• the dust binder may also already be a constituent of the seed-dressing composition.
• Anti-dusting agents used are silicone oil emulsions, for example. Silicone oil emulsions can reduce abrasion by a lubrication effect, and increase seed flow during application. This is described, for example, in WO 2012/168210. However, silicone oil emulsions have the disadvantage that they lead to considerable cost and inconvenience associated with cleaning of the seed-dressing system since the silicone oils present are insoluble in water and most of the customary cleaning solvents.
• U.S. Pat. No. 7,081,436 discloses seed treatment compositions which, to reduce dust formation, contain hydrocarbonoils having a boiling point of at least 150° C. as sticker.
• Preferred stickers disclosed are vegetable oil, for example rapeseed oil, petroleum-based hydrocarbon oils, paraffinic/naphthenic hydrocarbon oils, mineral oil, and mixtures thereof. These compounds too have the disadvantage of being insoluble in water, which complicates the cleaning of the seed-dressing system. In order to improve the water solubility, it would also be conceivable to use emulsifiers or to increase the amount of emulsifiers used. But this can have an adverse effect on the stability of the crop protection formulations.
• 7,081,436 additionally discloses the use of polyether-modified siloxanes in seed treatment compositions.
• the polyether-modified siloxanes are used with the aim of improving the colour intensity of the pigments present in the seed treatment composition and of assuring uniform coating of the seed treatment composition.
• the polyether-modified siloxanes are not used to reduce dust formation. They are thus not used as dust binders.
• the prior art anti-dusting agents thus have various disadvantages.
• the problem addressed by the present invention was therefore that of overcoming at least one disadvantage of the prior art.
• a particular problem addressed was that of providing an anti-dusting agent that reduces the evolution of dust in seed, and can additionally be readily removed with water in the cleaning of the seed-dressing system.
• Polyether-modified siloxanes lead to a reduction in the evolution of dust and are thus suitable as dust binders. They have the advantage of being water-soluble or water-emulsifiable. Systems that have come into contact with the compounds used as intended can thus be cleaned with water in an environmentally friendly manner. The use of additional emulsifiers that can have an adverse effect on the stability of crop protection formulations can be reduced or even avoided. There is also no need to use any organic solvents for cleaning.
• the number-average molecular weight M N is determined by means of gel permeation chromatography (GPC) as per standard DIN 55672:2016, preferably as per standard DIN 55672-1:2016.
• GPC gel permeation chromatography
• the divalent units (OC 2 H 3 R 3 ) in formulae (II) and (III) and [CH 2 CH(CH 3 )O] in formula (IV) may be bonded differently to the adjacent groups or atoms.
• (OC 2 H 3 R 3 ) is in each case independently a radical of the [CH 2 CH(R 3 )O] form and/or of the [CH(R 3 )CH 2 O] form, but preferably a radical of the [CH 2 CH(R 3 )O] form.
• [CH 2 CH(CH 3 )O] in formula (IV) is in each case independently a radical of the [CH 2 CH(CH 3 )O] form and/or of the [CH(CH 3 )CH 2 O] form, but preferably a radical of the formula [CH 2 CH(CH 3 )O].
• the formulae (I), (II) (III) and (IV) describe compounds that are constructed from repeat units, for example repeating fragments, blocks or monomer units, and may have a molar mass distribution. The frequency of the repeat units is reported by indices. The corresponding indices are the numerical average over all repeat units.
• the indices a, b, c, c(1), c(2), c(3), c(4) and optionally d used in the formulae should be regarded as statistical averages (number averages). Index d may alternatively be an integer.
• the indices a, b, c, c(1), c(2), c(3), c(4) and optionally d used and also the value ranges of the reported indices are thus understood to be averages of the possible statistical distribution of the structures that are actually present and/or mixtures thereof.
• the polyether-modified siloxanes to be used in accordance with the invention are preferably in the form of equilibrated mixtures. Specific embodiments may lead to restrictions to the statistical distributions as a result of the embodiment.
• the present invention firstly provides for the use of at least one polyether-modified siloxane as dust binder for seed.
• siloxane component of the polyether-modified siloxane similarly to the case of silicone oils, reduces dust formation, and the polyether component of the polyether-modified siloxane in turn enables solubility or emulsifiability in water.
• a polyether-modified siloxane is understood to mean a compound having organic radicals bonded to silicon atoms and structural units of the formula ⁇ Si—O—Si ⁇ , where “ ⁇ ” represents the three remaining valencies of the silicon atom in question and where at least one organic radical comprises a polyether radical.
• the R 1 or R and R 2 radicals may each be selected independently of one another and, compared in pairs, are the same or different.
• the at least one polyether-modified siloxane used has 41 to 81, preferably 43 to 75 and especially 45 to 70 silicon atoms.
• the at least one polyether-modified siloxane is a compound of the general formula (I)
• the divalent polyether radicals (OC 2 H 3 R 3 ) c are each independently selected from radicals of the general formula (III)
• the monovalent polyether radical R 2 of the general formula (II) comprises one or more divalent polyether radicals of the general formula (III) that are based on ethylene oxide, propylene oxide, butylene oxide and/or styrene oxide or mixtures thereof.
• R 2 is in each case independently selected from radicals of the general formula —CH 2 CH 2 CH 2 O[C 2 H 5 O] c(1) [CH 2 CH(CH 3 )O] c(2) H.
• the corresponding polyether-modified siloxane is obtainable, for example, by hydrosilylation of a terminally unsaturated polyether of the general formula CH ⁇ CHCH 2 O[C 2 H 5 O] c(1) [CH 2 CH(CH 3 )O] c(2) H, with an SiH-functional siloxane.
• R 2 thus derives from a terminally unsaturated polyether of the general formula CH ⁇ CHCH 2 O[C 2 H 5 O] c(1) [CH 2 CH(CH 3 )O] c(2) H, where the polyether is in turn obtainable from the reaction of ethylene oxide and optionally propylene oxide with allyl alcohol.
• the proportion by mass of oxyethylene groups (OC 2 H 4 ) based on the total mass of all (OC 2 H 3 R 3 ) groups in the polyether-modified siloxane is from 35% to 95%, preferably from 40% to 90%, especially from 45% to 85%.
• the number-average molecular weight M N of R 2 is from 200 g/mol to 2500 g/mol, preferably from 400 g/mol to 2000 g/mol, especially from 500 g/mol to 1500 g/mol.
• the number-average molecular weight M N of R 2 is defined here as the number-average molecular weight M N of the corresponding unsaturated polyether used in the preparation of the polyether-modified siloxane and is determined by means of gel permeation chromatography (GPC) to standard DIN 55672:2016, preferably to standard DIN 55672-1:2016.
• the divalent polyether radical (OC 2 H 3 R 3 ) c or the polyether radical R 2 calculated without the Z radical and without the OR 4 radical has a molar mass M(PE) of 140 g/mol to 2460 g/mol, preferably of 360 g/mol to 1940 g/mol, especially of 440 g/mol to 1460 g/mol.
• the molar mass M(PE) is calculated by the equation:
• Z is in each case independently selected from the group consisting of (d+1)-valent hydrocarbyl radicals that are optionally interrupted by oxygen atoms and have 2 to 10, preferably 3 to 4 and especially 3 carbon atoms. It is further preferable that Z is a divalent or trivalent radical. Z is preferably selected from the group consisting of:
• the polyether-modified siloxanes to be used in accordance with the invention have a cloud point of greater than 30° C.
• the cloud point can be determined as for mineral oil products according to standard DIN EN 23015:1994-05 or standard DIN EN ISO 3015:2018-04.
• the polyether-modified siloxanes used are largely or completely biodegradable.
• Biodegradability here is preferably determined by the OECD 301 F method. More preferably, biodegradability is determined in accordance with OECD 301 F after 28 days at 22° C. Further preferably, biodegradability is determined as in EP 3106033 A1, especially as described in the examples therein. It is preferable here that the polyether-modified siloxanes have a biodegradability of not less than 60%, especially of not less than 65%, the maximum value being 100%.
• the polyether-modified siloxanes can be obtained, for example, in the manner known to the person skilled in the art by hydrosilylation from the corresponding unsaturated polyethers and the corresponding SiH-functional siloxanes.
• the process preferably used for preparation of the polyether-modified siloxanes according to the invention is a transition metal-catalysed hydrosilylation of the unsaturated polyethers with SiH-functional siloxanes to form Si—C linkages, as described, for example, in EP 1520870, EP 1439200, EP 1544235, U.S. Pat. Nos. 4,147,847, 4,025,456, EP 0493836 or U.S. Pat. No. 4,855,379 and the documents cited therein.
• the polyether-modified siloxanes are used as dust binders for seed.
• a dust binder reduces dust formation in seed that has been treated with a seed-dressing composition or a seed-dressing liquor.
• a measure preferably employed for the dust binding capacity, i.e. for the reduction in the evolution of dust, and hence for the efficacy of an additive as dust binder, is the dust value, which is determined with the aid of the Heubach test (ESA 11.0387, ESA STAT Dust Working Group, Version 1.0 of 23.03.2011) as described in the examples. If the dust value can be lowered by the addition of the additive to the seed-dressing composition or to the seed-dressing liquor, the additive is a suitable dust binder. For this purpose, the dust value of seed that has been treated with a seed-dressing liquor containing the additive is compared to the dust value of seed that has been treated in the same way but with a seed-dressing liquor that does not contain the additive.
• the binding of dust in the seed treated can be adjusted via the amount of the polyether-modified siloxane.
• the at least one polyether-modified siloxane is used in such a way that the proportion by mass of the at least one polyether-modified siloxane based on the total mass of the treated seed is from 0.001 ppm to 1000 ppm, preferably 0.01 ppm to 100 ppm, especially 0.1 ppm to 10 ppm.
• Seed is understood by the person skilled in the art to mean dry, dormant, generative propagation organs such as seeds, fruits, accessory fruits, infructescences or parts thereof. They contain the complete germ of the plants that has resulted from pollination.
• the seed used preferably comprises grains from the grass family.
• the grains are especially preferably selected from the group consisting of the grains of wheat, rye, barley, oats, triticale, rice, maize and millet/sorghum.
• the seed is treated as described by way of introduction.
• the invention therefore further provides a method of reducing dust formation in seed, comprising the steps of:
• the polyether-modified siloxane may be part here of the seed-dressing liquor or of the seed-dressing composition.
• the invention therefore further provides a seed-dressing liquor or a seed-dressing composition comprising the at least one polyether-modified siloxane.
• the polyether-modified siloxanes used as intended are preferably used in aqueous compositions.
• the compositions used as intended i.e. the seed-dressing composition or seed-dressing liquor, preferably do not include any emulsifiers. It is further preferable that the compositions used as intended include further ingredients selected from fungicides, insecticides, pesticides, herbicides, nematicides, fertilizers, nutrients, microorganisms, stickers, pigments, surfactants, dispersants (dispersing agents), free-flow aids and defoamers.
• the seed-dressing liquor is preferably an aqueous dilute dispersion or emulsion.
• the seed-dressing liquor preferably comprises:
• ingredients listed above i.e. the fungicides, insecticides, pesticides, herbicides, nematicides, fertilizers, nutrients, microorganisms, stickers, pigments, surfactants, dispersants, free-flow aids or defoamers, and the polyether-modified siloxane, are preferably part of the seed-dressing composition, but may also be added to the seed-dressing liquor as a further additive.
• the seed is initially introduced into the mixing drum (seed drum) of a seed-dressing system and the seed-dressing liquor is added continuously or batchwise and mixed with the seed.
• the seed-dressing liquor is preferably sprayed here by means of an impeller plate in the mixing drum containing the seed.
• the seed is introduced into the mixing drum, the impeller plate is started and the liquor is sprayed in.
• the seed-dressing operation has preferably ended after 30 seconds. This may be followed by a drying process in which the water is removed. There is preferably no active removal of the water.
• the treated seed has preferably been coated homogeneously with the nonaqueous constituents of the seed-dressing liquor.
• the treated seed is subsequently preferably bagged and supplied to the user in that form.
• the invention therefore further provides treated seed obtainable by the inventive use of the at least one polyether-modified siloxane and/or the method according to the invention.
• the invention therefore also further provides treated seed comprising seed and the at least one polyether-modified siloxane.
• the determination of the dust values is conducted by the ESA 11.0387 (ESA STAT Dust Working Group, Version 1.0 of 23.03.2011) method. This involves conducting the Heubach test “Assessment of free floating dust and abrasion particles of treated seeds as a parameter of the quality of treated seeds” with a dustmeter from Heubach, type 1, according to the instructions.
• the Heubach test is the standard test conducted in industry for determining the dusting tendency of dressed seed.
• the adhesion or abrasion of the seed-dressing composition on the seed is measured. This is done by introducing 100 g of dressed seed into a drum that subsequently rotates. This subjects the seed to mechanical stress; an air stream is guided through the system.
• the seed dusts detached are sucked onto a filter unit, and the filter is weighed.
• the result is the Heubach value, which is often reported in g of dust per dt of dressed seed, but also g of dust per 100 000 seed grains.
• a calculated value of g of dust per ha is often also found.
• the siloxanes can be characterized with the aid of 1 H NMR and 29 Si NMR spectroscopy. These methods, especially taking account of the multiplicity of the couplings, are familiar to the person skilled in the art.
• the SiH values of the SiH-functional siloxanes used, and also those of the reaction matrices, are determined in each case using a gas-volumetric method by the sodium butoxide-induced decomposition of weighed aliquots of samples, using a gas burette.
• the hydrogen volumes measured are inserted into the general gas equation, they allow determination of content of active SiH functions in the starting materials, and also in the reaction mixtures, and thus allow monitoring of conversion.
• a solution of sodium butoxide in butanol is used (5% by weight of sodium butoxide).
• the mixture was filtered, A dear liquid was obtained.
• the siloxane obtained was characterized with the aid of 29 Si NMR spectroscopy.
• An SiH-functional siloxane of the empirical formula Me 3 SiO[SiMe 2 O] 38 [SiMeHO] 10 SiMe 3 was obtained.
• the SiH-functional siloxane was reacted with an unsaturated polyether in a hydrosilylation reaction.
• the hydrosilylation reaction was conducted in the presence of a complete platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution in xylene (purchased from Sigma-Aldrich, Pt content: 2% by weight) as Karstedt catalyst.
• the hydrosilylation reaction was brought to full conversion in relation to the hydrogen content of the SiH-functional siloxanes.
• a full conversion is understood to mean that more than 99% of the SiH functions were converted. Detection is effected in the manner familiar to the person skilled in the art by gas-volumetric means after alkaline breakdown.
• an SiH-functional siloxane of the empirical formula Me 3 SiO[SiMe 2 O] 20 [SiMeHO] 5.5 SiMe 3 was first prepared and then reacted in a hydrosilylation reaction with a polyether of the empirical formula CH 2 ⁇ CHCH 2 O[C 2 H 5 O] 12.5 [CH 2 CH(CH 3 )O] 3.3 H.
• the seed dressings were blended with the additives to be examined for their dust-reducing effect by simply blending water and a commercial suspension concentrate for seed treatment for wheat and barley (Landor® CT from Syngenta).
• Additives examined were the polyether-modified siloxane from Example 1 and 2, a commercially available polyether-modified siloxane from Momentive (Example 3), the commercially available anti-dusting agent MaximalFlow® from BASF (Example 4), and a further additive based on a silicone oil emulsion (Example 5).
• the Landor® CT suspension concentrate used is a mixture of fludioxonil, difenoconazole and tebuconazole for treatment of seed, for example wheat and barley. It was used in the customary amount of 200 ml per 100 kg of seed. The amount of water used was likewise 200 ml per 100 kg of seed.
• the amounts of the additives used can be found in Table 1. MaximalFlow® (Example 4) was used in the amount recommended by the manufacturer of 20 ml per 100 kg of seed.
• the polyether-modified polyethersiloxanes were correspondingly likewise used at 20 ml per 100 kg of seed, and Example 1 additionally also at 10 ml per 100 kg of seed.
• the silicone oil-based additive of Example 5 (a 35% silicone oil emulsion) was used in an amount of 60 ml per 100 kg of seed.
• the seed-dressing liquors thus produced were applied to 1 kg of seed (wheat) in each case by means of a standard seed-dressing system (mixing system based on the rotor-stator principle). Subsequently, by means of the Heubach test, the dust values reported in g of dust per 100 kg of seed were determined (see Table 1).
• compositions of the seed-dressing liquors (dressings) (stated amounts of the components in ml per 100 kg of seed); dust values of the dressed seeds according to Heubach test (figures in g of dust per 100 kg of seed, ESA 11.0387, ch.
• the polyether-modified siloxanes also have the advantage that the mixing drum of the seed-dressing system can be cleaned with water without difficulty, i.e. all residues of the dressing are easy to remove.
• Examples 4 and 5 based on silicone oil emulsions present difficulties here since the silicone oil present leads to tacky residues that are difficult to remove.

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• Life Sciences & Earth Sciences (AREA)
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• Wood Science & Technology (AREA)
• Pest Control & Pesticides (AREA)
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