Dispersants

Abstract

The subject of the present invention is a composition containing a compound of formula (I), formula (II) or a mixture thereof TIFF2022517822000016.tif66170[In the formula, n is an integer equal to or greater than 1, R 1 is an aliphatic linear or branched hydrocarbon residue having 1 to 10 carbon atoms, a hydrogen atom, the structural unit -OX or the structural unit -CH-OX, X corresponds to formula (III) TIFF2022517822000017.tif48170 (in the formula, a is an integer from 2 to 6, b is an integer from 0 to 3, c is an integer from 20 to 28; m is 1 or 2; R 2 is an aliphatic linear or branched hydrocarbon residue having 1 to 10 carbon atoms, Y is hydrogen, -SO3M, -SO2M, -PO3M2, or -CH2COOM, and M is a cation). The compounds of formula (I), (II), or mixtures thereof are particularly suitable to act as dispersants.

Description

[Technical Field]

[0001] The subject of the present invention is branched and block polymeric dispersants.They are suitable for emulsifying or dispersing solid and liquid materials in aqueous liquids.For example, the dispersants according to the present invention can be used to prepare aqueous pigment preparations of organic and inorganic pigments or aqueous preparations of plant protection agents. [Background technology]

[0002] Various dispersants having block copolymer structures are known in the prior art.

[0003] EP 3260480 describes the advantages of blocky arrangements of various monomers over random arrangements in the use of such polymers as dispersants. These polymers are obtained by radical polymerization techniques.

[0004] EP1078946 (Patent Document 2) discloses compounds of structure R 1 as low foaming wetting and dispersing agents. 1 O(SO) a (EO) b (PO) c (BO) d R 2 They describe linear block polyalkylene oxides of the formula: They are obtained by anionic ring-opening polymerization. 1 R represents a linear, branched or alicyclic residue having 8 to 13 carbon atoms. 2 is hydrogen, an acyl residue, an alkyl residue, or a carboxylic acid residue (each having 1 to 8 carbon atoms); SO is styrene oxide; EO is ethylene oxide; PO is propylene oxide; BO is butylene oxide; a is 0 to 1.9; b is 3 to 50; c is 0 to 3; and d is 0 to 3.

[0005] EP 0 940 406 (Patent Document 3) discloses, inter alia, the use of phosphate esters obtained by converting ω-hydroxy-functional oligo- or poly(alkyl)styrenes into poly(alkyl)styrene-block(b)-polyalkylene oxide copolymers, which are then converted into the corresponding phosphate esters. Here again, linear polymers are disclosed.

[0006] DE 102006002800 (Patent Document 4) discloses dispersants based on copolymers of styrene oxide, alkylene oxide, and divalent or higher amines and alcohols. This results in a branched, blocky structure that allows for the production of liquid, low-viscosity, foam-free pigment dispersions. Low-molecular-weight initiator molecules with molecular weights of less than 65 g / mol are described as particularly suitable (Examples 1-4). Such molecules can be, for example, ethylene glycol (a dihydric alcohol) or ethylenediamine. However, a solvent is required during production to achieve the desired tank filling level before the addition of styrene oxide.

[0007] Because ring-opening anionic polymerization is highly exothermic and releases a lot of heat, styrene oxide must be added slowly. Therefore, in these cases, a solvent is required to ensure a tank fill level that allows for efficient mixing and agitation. For example, such a solvent is bis(2-methoxyethyl) ether (diglyme). This solvent, in turn, generates volatile organic components in the dispersion unless removed at great expense. Given increasingly stringent government regulations and growing consumer awareness in the colorant and paint industries, such volatile components (volatile organic compounds, or VOCs, and semi-volatile organic compounds, or SVOCs) should, at best, be completely avoided in order for the resulting colorant to still qualify for eco-labeling. Dispersants, in particular, should be free of such volatile components, since VOC / SVOC components cannot be completely eliminated in the case of other components (binders, coalescing agents), and colorant manufacturers must therefore maintain formulation flexibility. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] EP3260480 [Patent Document 2] EP1078946 [Patent Document 3] EP0940406 [Patent Document 4] DE102006002800 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, the object of the present invention was to provide a VOC- and SVOC-free dispersant for use in, for example, pigment preparations or for producing dispersion-type plant protection formulations. In the case of pigment preparations, these should have high tinting strength and low viscosity. Furthermore, the essential coating properties should not be negatively affected. For example, compatibility with base paints, which is tested using the so-called rub-out test, should be mentioned. Therefore, rub-out should be as low as possible.

[0010] Pesticides are usually used in the form of preparations to achieve better utilization of the active substance. Such preparations, also called formulations, are generally in solid or liquid form. Liquid pesticide preparations have the advantage that they can be easily measured by the user and can be uniformly dispersed in the spray broth. Modern pesticides are mostly complex organic molecules that are only slightly soluble in water or another solvent. Therefore, these pesticides are conveniently provided in a dispersed form as a suspension concentrate.

[0011] In these dispersion-type plant protection formulations, especially suspension concentrates, the solid active substance must be dispersed efficiently and finely, and sedimentation must be prevented. The fine particle size of the active substance ensures that the active substance can be taken up by the plant or target organism. In the case of emulsifiable concentrates, a hydrophobic solvent and a pesticide active substance dissolved therein, a wetting agent, and an emulsifying dispersant are prepared as a concentrate, and for application, an aqueous spray broth is prepared by dilution with a water-containing liquid, in which the hydrophobic solvent and the active substance are emulsified.

[0012] Dispersants are required for the stabilization of pesticides in suspension concentrates. These dispersants, optionally supported by suitable surface-active substances (wetting agents), allow the production of suspension concentrates, which is usually achieved by means of milling to provide high mechanical forces to the system. After the milling process, the dispersants have a stabilizing effect on the system by steric or electrostatic interactions. Dispersants can be anionic, cationic, amphoteric or nonionic in structure. They can be of low molecular weight nature or can be the product of polymerized monomers. Random The polymers may be higher molecular weight polymers that form alternating, block, comb, or star-shaped configurations.

[0013] Examples of commercially important dispersants used in large quantities for the production of suspension concentrates are sulfonated condensation products of alkylnaphthalenes and formaldehyde (naphthalenesulfonates) or ligninsulfonates. However, these products irritate the skin and eyes, and therefore no longer meet the current requirements for toxicological harmlessness and user safety. Furthermore, to obtain stable suspension concentrates, these dispersants are not particularly effective, i.e., they require relatively large amounts.

[0014] It was therefore an object of the present invention to provide a suspension concentrate based on a dispersant which allows sufficient stabilization of the suspension concentrate even in small amounts, is easy to process, is preferably present in liquid form and is characterized by an advantageous toxicological profile. [Means for solving the problem]

[0015] Surprisingly, this problem has been particularly well solved by branched polymer structures that are alkylene oxide addition products initiated from trihydric or higher polyols: they are block copolymers containing structural units composed of polyol, styrene oxide, and at least one alkylene oxide.

[0016] Due to the at least trivalent starting material molecules, these polymers have a star-shaped or dendrimer-type structure with a rather hydrophobic core and a rather hydrophilic periphery. The use of other starting material molecules and a different composition or block sequence than those mentioned above leads to dispersants that do not have all of the above-mentioned property profiles (especially with regard to volatile organic content and color properties as well as viscosity, stability and compatibility) when used in pigment preparations and plant protection formulations.

[0017] The subject of the present invention is a composition containing a compound of formula (I), formula (II) or a mixture thereof

[0018] [ka] [In the formula, n is an integer equal to or greater than 1, R 1 is an aliphatic linear or branched hydrocarbon residue having 1 to 10 carbon atoms, a hydrogen atom, the structural unit -OX, or the structural unit -CH2-OX, X corresponds to formula (III)

[0019] [ka] (In the formula, a is an integer from 2 to 6, b is an integer from 0 to 3, c is an integer from 20 to 28; m is 1 or 2; R 2 is an aliphatic linear or branched hydrocarbon residue having 1 to 10 carbon atoms, Y is hydrogen, -SO3M, -SO2M, -PO3M2, or -CH2COOM, and M is a cation).

[0020] The compounds of formula (I), the compounds of formula (II), or mixtures thereof are particularly suitable for acting as emulsifiers or dispersants. Hereinafter, they are referred to as dispersants according to the invention or dispersants according to the invention. The emulsifying or dispersing action is particularly for dispersing hydrophobic solvents or pesticides (in both cases in water-containing liquids), as well as inorganic or organic pigments in water-containing liquids.

[0021] The subject of the present invention is also the use of compounds of formula (I), formula (II) or mixtures thereof as emulsifiers or dispersants for hydrophobic solvents or for dispersing pesticides in water-containing liquids.

[0022] A further object of the present invention is a method for the emulsification or dispersion of at least one hydrophobic solvent or pesticide in a water-containing liquid by adding to a mixture of the hydrophobic solvent or pesticide and the water-containing liquid at least one dispersant of formula (I) or (II).

[0023] A further subject of the present invention is a process for the preparation of compounds of formula (I), formula (II) or mixtures thereof, comprising 1. Formal replacement of residue X with H to provide an alcohol resulting from formula I or formula II, 2. This is combined with 2 to 6 moles of styrene oxide per active hydrogen, and optionally up to 3 moles, particularly 0 to 2 moles, and especially 0 to 1 mole of C3-C6 per active hydrogen. 12 - alkoxylated with alkylene oxide, wherein the alkoxylation is carried out with styrene oxide and the C3-C 12 - alkylene oxides, which can be carried out simultaneously or sequentially, 3. Optionally repeat step 2 once or twice; and 4. Alkoxylation of the product thus obtained with 20 to 28 moles of ethylene oxide per active hydrogen, This is the method.

[0024] If step 2 is repeated once or twice, the styrene oxide and C3-C 12 It should be noted that the molar amounts a and b of alkylene oxide are in the ranges given above.

[0025] The alkoxylation is carried out using alkali metal, alkaline earth metal or bimetal cyanide catalysts. Typical reaction temperatures are in the range of 130-140°C. The reaction is typically carried out under inert conditions (using a nitrogen blanket) at a pressure of 2-9 bar.

[0026] In formula (III), the wavy line indicates the point of attachment of this residue to the rest of the molecule (formula I or II). Starting from this bond, it is necessary that the structural unit with stoichiometric index m always precedes the structural unit with stoichiometric index c, i.e., the polyol starting material always first reacts with styrene oxide and / or an alkylene oxide other than ethylene oxide before ethylene oxide is prepolymerized. On the other hand, the block with stoichiometric index a and b in brackets with stoichiometric index m Randomly Or they may be arranged in a block fashion.

[0027] In a preferred embodiment, a is the number 3, 4 or 5, in particular 3 or 4.

[0028] In a preferred embodiment, b is a number from 0 to 2, in particular 0 or 1.

[0029] In a preferred embodiment, m is 1.

[0030] In a preferred embodiment, Y is H or -PO3M2.

[0031] In a preferred embodiment, a is 3, 4 or 5, particularly 3 or 4, b is 0 or 1, and the ratio of (a+b):c is 1:4 to 1:6.

[0032] In a preferred embodiment, M is hydrogen, Na + , K. + , NH4 + , triethanolammonium, or a combination thereof.

[0033] In a preferred embodiment, the composition according to the invention comprises a compound of formula I and / or II, wherein a is a number between 2 and 6, b is a number from 0 to 3, c is a number between 20 and 28, m is the number 1 or 2, especially 1, and Y is H or -PO3M2 Contains compounds.

[0034] In a further preferred embodiment, the dispersant corresponds to formula (I) wherein a is a number from 2 to 6, b is 0 or 1, m is 1, and c is a number from 20 to 28.

[0035] In a preferred embodiment, R 1 is -CH2-OX.

[0036] In a preferred embodiment, n is 1.

[0037] In a preferred embodiment, R 2 is CH3.

[0038] In all the above embodiments, a is especially 3, 4 or 5, especially 3 or 4.

[0039] The dispersants according to the present invention are prepared by the addition and anionic polymerization of styrene oxide, ethylene oxide, propylene oxide, butylene oxide or long-chain alkylene oxide to polyols. Alkoxylation is carried out on one or more oxygen atoms of these polyols. The alkoxylation is carried out in a deactivated manner using known catalysts, such as alkali metal, alkaline earth metal or bimetal cyanide catalysts. Typical temperatures are in the range of 130-140°C, and typical pressures are in the range of 2-9 bar. The anionic polymerization is carried out in the following manner: random (within block m), or blockwise (within block m and with respect to m relative to c).

[0040] If the ratio of monomer to initiator molecules is too high to ensure adequate mixing of the initiator and catalyst at the start of the reaction, the synthesis can be carried out using a co-solvent, which can be a glycol, glycol ether, glyme, or other organic solvent.

[0041] However, the dispersant according to the present invention can also be produced in bulk without a solvent. At the end of the reaction, the catalyst must optionally be neutralized. This can be done with a common acid, such as an organic carboxylic acid (e.g., acetic acid, lactic acid, isononanoic acid) or an inorganic acid (mineral acid).

[0042] The polymer formulation can be in bulk (highly viscous liquid) or in solution. Residual solvents from the synthesis may be present in the solution. In contrast, aqueous formulations are preferred because they are easier to handle in the subsequent production of pigment dispersions or plant protection agents due to their lower viscosity. This also ensures that volatile organic compounds (VOC / SVOC) are not introduced into the final composition obtained when using the dispersant according to the invention.

[0043] Following copolymerization, the nonionic dispersants of formula (I) or (II) produced in the first step can be modified by the addition of anionic groups. Suitable anionic groups are sulfuric acid half esters, which can be obtained by reacting the nonionic dispersants of the invention with amidosulfonic acids, or phosphate esters, which are prepared by reacting the nonionic dispersants of the invention with orthophosphoric acid, polyphosphoric acid, or phosphorus pentoxide P2O5. Ether carboxylic acids can be prepared by reacting the nonionic dispersants of the invention with monochloroacetic acid under alkaline conditions.

[0044] In a particularly preferred embodiment, the dispersant according to the present invention is mixed with an 80% aqueous system after synthesis and neutralized with lactic acid. Lactic acid has a pKa value of 3.90 and has the advantage of being extremely odorless compared to other organic acids, such as acetic acid. This method is particularly preferred for dispersants according to the present invention, in which a is a number from 2 to 6, b is 0, m is 1, and c is a number from 20 to 28.

[0045] In a particularly preferred embodiment, the dispersant of the present invention (wherein a is a number from 2 to 6, b is 0, and c is a number from 20 to 28) is modified at the end of the reaction so that Y is a phosphate.

[0046] The dispersants according to the present invention are suitable for dispersing at least one solid pesticide in a water-containing liquid by adding at least one dispersant of formula (I) or (II) to a hydrophobic solvent or a mixture of a pesticide and a water-containing liquid, and the emulsion or dispersion thus produced is (A) 3 to 80% by weight, in particular 20 to 70% by weight, and more particularly 30 to 65% by weight, of at least one hydrophobic solvent or pesticide, (B) 0.1 to 30% by weight, in particular 1 to 15% by weight, of at least one dispersant of formula (I) and / or (II), (C) 5 to 99% by weight, particularly 5 to 90% by weight, and particularly preferably 10 to 70% by weight of water Contains:

[0047] The pesticide(s) of component (A) of the aqueous formulation of the plant protection agent according to the invention are in particular selected from the group consisting of herbicides, insecticides and fungicides.

[0048] Preferred fungicides are aliphatic nitrogen-based fungicides, amide fungicides, such as acylamino acid fungicides, or anilide fungicides, or benzamide fungicides, or strobilurin fungicides, aromatic fungicides, benzimidazole fungicides, benzothiazole fungicides, carbamate fungicides, conazole fungicides, such as imidazoles or triazoles, dicarboximide fungicides, dithiocarbamate fungicides, imidazole fungicides, morpholine fungicides, oxazole fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quinone fungicides.

[0049] Preferred herbicides include amide herbicides, anilide herbicides, aromatic acid herbicides, such as benzoic acid herbicides or picolinic acid herbicides, benzoylcyclohexanedione herbicides, benzofuranyl alkylsulfonate herbicides, benzothiazole herbicides, carbamate herbicides, carbanilate herbicides, cyclohexene oxime herbicides, cyclopropylisoxazole herbicides, dicarboximide herbicides, dinitroaniline herbicides, dinitrophenol herbicides, diphenyl ether herbicides, dithiocarbamate herbicides, imidazolinone herbicides, nitrile herbicides, organophosphate herbicides, and oxadiazolone herbicides. , oxazole herbicides, phenoxy herbicides, such as phenoxyacetic acid herbicides, or phenoxybutanoic acid herbicides, or phenoxypropionic acid herbicides, or aryloxyphenoxypropionic acid herbicides, pyrazole herbicides, such as benzoylpyrazole herbicides, or phenylpyrazole herbicides, pyridazinone herbicides, pyridine herbicides, thiocarbamate herbicides, triazine herbicides, triazinone herbicides, triazole herbicides, triazolone herbicides, triazolopyrimidine herbicides, uracil herbicides, urea herbicides, such as phenylurea herbicides, or sulfonylurea herbicides.

[0050] Preferred insecticides are carbamate insecticides, such as benzofuranylmethylcarbamate insecticides or dimethylcarbamate insecticides or oximecarbamate insecticides or phenylmethylcarbamate insecticides, diamide insecticides, insect growth regulators, macrocyclic lactone insecticides, such as avermectin insecticides, or milbemycin insecticides, or spinosyn insecticides, nereistoxin analogue insecticides, nicotinoid insecticides, such as nitroguanidine nicotinoid. or pyridylmethylamine nicotinoid insecticides, organophosphorus insecticides such as organophosphate insecticides, or organothiophosphate insecticides, or phosphonate insecticides, or phosphoramidothioate insecticides, oxadiazine insecticides, pyrazole insecticides, pyrethroid insecticides such as pyrethroid ester insecticides, pyrethroid ether insecticides, or pyrethroid oxime insecticides, tetramic acid insecticides, tetrahydrofurandione insecticides, and thiazole insecticides.

[0051] Particularly preferably, the pesticide or pesticides of component a) of the suspension concentrate according to the invention are selected from the group consisting of triazole fungicides, strobilurin fungicides, neonicotinoid insecticides, phenylpyrazole insecticides, benzoylcyclohexanedione herbicides, triazine herbicides and sulfonylurea herbicides.

[0052] Particularly preferably, the one or more pesticides of component a) of the suspension concentrate according to the invention are selected from the group consisting of epoxiconazole, tebuconazole, azoxystrobin, trifloxystrobin, imidacloprid, thiacloprid, thiamethoxam, fipronil, ethiprole, mesotrione, tembotrione, atrazine, nicosulfuron, iodosulfuron and mesosulfuron.

[0053] The dispersants according to the invention are also particularly suitable for the production of pigment preparations using organic and / or inorganic pigments. In an exemplary composition, the pigment preparations produced in this way may have the following components: (A) 3 to 80% by weight, in particular 20 to 70% by weight, more particularly 30 to 65% by weight, of at least one organic and / or inorganic pigment. (B) 0.1 to 30% by weight, in particular 1 to 15% by weight, of at least one dispersant of formula (I) and / or (II). (C) 0 to 50% by weight, in particular 1 to 20% by weight, of a wetting agent, typically a polyethylene glycol ether having an average molar mass of 200 to 2000 g / mol. (D) 0 to 2% by weight, particularly 0.02 to 0.5% by weight, of an antifoaming agent. (E) 0 to 2% by weight, in particular 0.02 to 0.2% by weight, of a preservative substance. (F) 5 to 90% by weight, particularly 10 to 70% by weight, of water.

[0054] Component (A) of the pigment preparation is in particular a finely divided organic or inorganic pigment or a mixture of different organic and / or inorganic pigments, which can be used in the form of a dry powder, as granules or as a water-moist presscake.

[0055] The pigment preparations prepared using the dispersants of the present invention have good storage stability and very little tendency to flocculate and settle. They have high tinting strength, clear color tone, and low viscosity. They are compatible with common aqueous coating systems, such as high-pigment volume concentration emulsion paints and low-pigment volume concentration emulsion paints.

[0056] Plant protection formulations containing solid pesticides can be prepared as follows: Typical methods for producing suspension concentrates: Thickeners used for rheology adjustment, e.g. Kelzan (登録商標) All components except for the S solution are pre-dispersed in a dissolver. Subsequent milling is carried out in a bead mill until the desired particle size is reached. (登録商標) Add S aqueous solution to adjust to desired final viscosity.

[0057] In the case of emulsifiable concentrates, a water-immiscible solvent is mixed with one or more pesticidal active agents, dispersants, and additional ingredients to form a concentrate, which is emulsified by dilution with a water-containing liquid to form a spray broth.

[0058] Pigment preparations can be prepared using the dispersants of the present invention by dispersing component (A) in the form of a powder, granules, or aqueous presscake in the presence of water and components B, and optionally (C), (D), and (E), in a manner customary per se, followed by optional mixing with water and adjusting the resulting aqueous pigment dispersion to the desired concentration with water. Specifically, components (B), (C), (D), (E), and (F) are mixed and homogenized, and then component (A) is stirred into the charged mixture to form a paste and predisperse the pigment. Depending on the particle hardness of the granules used, they are subsequently finely dispersed or refined using a grinding or dispersing device, optionally under cooling. For this purpose, stirrers, dissolvers (saw-tooth stirrers), rotor-stator mills, ball mills, stirring ball mills, such as sand mills and bead mills, high-speed mixers, kneading devices, roll mills, or high-performance bead mills can be used. The microdispersion or grinding of the pigment is carried out until the desired particle size distribution is achieved and can be carried out at a temperature in the range of 0 to 100° C., suitably between 20 and 60° C. Following microdispersion, the pigment preparation may be further diluted with water, in particular with deionized or distilled water.

[0059] Pigment preparations which contain the dispersants according to the invention are particularly suitable for the pigmentation or production of paints and emulsion paints and dispersion varnishes, which are used for facade painting.

[0060] Dispersants according to the invention are free of alkylphenols and alkylphenol ethoxylates and therefore waste containing dispersants according to the invention is not harmful to aquatic life. [Example]

[0061] example Synthesis of Samples 1-3 and Comparative Samples 1-4 Sample 1: Pentaerythritol + 4 mol propylene oxide + 12 mol styrene oxide + 80 mol ethylene oxide A 1 L glass autoclave was charged with the reaction product of pentaerythritol and 4 equivalents of propylene oxide (150.0 g, 0.41 mol) together with potassium hydroxide (40% by weight in water; 2.40 g). The mixture was dried under vacuum at 125 °C for 1 hour. Subsequently, styrene oxide (587.1 g, 4.89 mol) was added in portions at this temperature. The reaction was checked by titration of the epoxide value. The intermediate product was then cooled to 100 °C and isolated. The intermediate product (250.0 g, 0.14 mol) was then recharged into a 1 L glass autoclave heated to 125 °C. At this temperature, 486.7 g (11.05 mol) of ethylene oxide were metered in portions at a total pressure of 2 to 5 bar in an inert operating mode. After reacting to a constant pressure, the product was cooled to 80° C. and vacuum was applied for 30 minutes to remove traces of unreacted ethylene oxide, and the product was isolated.

[0062] Sample 2: Glycerin + 12 mol styrene oxide + 75 mol ethylene oxide Glycerin (200 g, 2.17 mol) and KOH (40% aqueous solution, 30.46 g) were placed in a 1 L autoclave, and the mixture was heated at 120 °C for 2 hours and then heated to 130 °C. At this temperature, styrene oxide (521.9 g, 4.34 mol) was added in portions. The reaction was checked by titration of the epoxide value. The intermediate was isolated, and a portion (172.0 g, 0.51 mol) was added to a further reaction at 130 °C by adding styrene oxide (735.9 g, 6.12 mol) in portions. The reaction was checked by titration of the epoxide value. The intermediate product (200.0 g, 0.13 mol) was placed in an autoclave and reacted with ethylene oxide (459.5 g, 10.4 mol) at 135 °C in an inert operating mode at a total pressure of 2-6 bar. After reacting to a constant pressure, the product was cooled to 80° C. and vacuum was applied for 30 minutes to remove traces of unreacted ethylene oxide, and the product was isolated.

[0063] Sample 3: Glycerin + 12 mol styrene oxide + 75 mol ethylene oxide + sodium phosphate The precursor was prepared analogously to "Sample 2". Sample 2 (1730.7 g) was placed in a stirred apparatus and heated to 60 °C, after which polyphosphoric acid (117.1 g) was metered in over an addition time of 2.5 h. The internal temperature of the exothermic reaction ranged from 60 to 70 °C. After the addition was complete, the reaction was allowed to proceed for 1 h at 70 °C and for a further 5 h at 100 °C. The product was adjusted to a pH of 7.7 with caustic soda solution (50 wt. % aqueous solution) and a total water content of 20 wt. %.

[0064] Comparative sample 1: Ethylenediamine + 16 styrene oxide + 100 ethylene oxide Ethylenediamine (60.1 g) was dissolved in dimethyltetraglycol (294.5 g) and reacted with styrene oxide (480.6 g). Potassium hydroxide was added (15.0 g of a 40 wt % aqueous solution) and the contained water was removed in vacuo at 100°C. Subsequently, additional styrene oxide (1441.8 g) was added, and after the reaction was complete, the intermediate was isolated. In a subsequent reaction, the intermediate (341.6 g) was reacted with ethylene oxide (656.5 g). After the reaction was complete, the product was adjusted to a water content of 20% and isolated.

[0065] Comparative sample 2: Ethylenediamine + 4 propylene oxide + 8 styrene oxide + 80 ethylene oxide Similar to the synthesis described above, the reaction product of ethylenediamine and 4 equivalents of propylene oxide (200.0 g, 0.68 mol) was alkalized with potassium hydroxide (40 wt % in water; 5.59 g), dried, and reacted with styrene oxide (587.1 g, 4.89 mol) at 130 °C. The resulting intermediate product (220.0 g, 0.17 mol) was reacted with ethylene oxide (583.1 g, 13.24 mol) at 135 °C. After reaction to a constant pressure, the product was cooled to 80 °C and vacuum was applied for 30 minutes to remove traces of unreacted ethylene oxide, and the product was isolated.

[0066] Comparative sample 3: Pentaerythritol + 4 propylene oxide + 4 styrene oxide + 10 ethylene oxide Similar to the synthesis described above, the reaction product of pentaerythritol and 4 equivalents of propylene oxide (225.0 g, 0.61 mol) was alkalized with potassium hydroxide (40 wt % in water; 3.61 g), dried, and reacted with styrene oxide (293.5 g, 2.44 mol) at 130 °C. The resulting intermediate product (180.0 g, 0.21 mol) was reacted with ethylene oxide (373.6.7 g, 8.48 mol) at 135 °C. After reaction to a constant pressure, the product was cooled to 80 °C and vacuum was applied for 30 minutes to remove traces of unreacted ethylene oxide, and the product was isolated.

[0067] Comparative sample 4: Pentaerythritol + 4 propylene oxide + 8 styrene oxide + 140 ethylene oxide Similar to the synthesis described above, the reaction product of pentaerythritol and 4 equivalents of propylene oxide (225.0 g, 0.61 mol) was alkalized with potassium hydroxide (40 wt % in water; 3.61 g), dried, and reacted with styrene oxide (587.1 g, 4.89 mol) at 130 °C. The resulting intermediate product (180.0 g, 0.14 mol) was reacted with ethylene oxide (834.9 g, 18.95 mol) at 135 °C. After reaction to a constant pressure, the product was cooled to 80 °C and vacuum was applied for 30 minutes to remove traces of unreacted ethylene oxide, and the product was isolated.

[0068] Samples 1-3 of the present invention start with pentaerythritol or glycerin. Sample 1 was propoxylated once per alcohol group, followed by the addition of styrene oxide and ethylene oxide blocks. Samples 2-3 used glycerin as the starting material without propoxylation, and added first styrene oxide and then ethylene oxide.

[0069] Comparative Sample 1 contains ethylenediamine as a starting material molecule. Therefore, diglyme is required as a polymerization solvent. As a result, the polymeric dispersant thus obtained contains VOC / SVOC and therefore does not meet the requirements.

[0070] In the case of Comparative Sample 2, as in Sample 1 according to the invention, one propoxylation was carried out for each amine hydrogen. In this way, a starting material with a higher molecular weight can be produced, which eliminates the need for a solvent for the subsequent polymerization. Comparative Sample 2 is therefore VOC / SVOC-free. Because ethylenediamine is used as the starting material, Comparative Sample 2 is not according to the invention.

[0071] Comparative Sample 3 was prepared using the polyol starting material pentaerythritol, where a=1, i.e., the proportion of styrene oxide is lower than required according to the present invention.

[0072] Comparative Sample 4 was prepared using the polyol starting material, pentaerythritol, where c=35, i.e., the proportion of ethylene oxide is higher than required according to the present invention.

[0073] [Table 1]

[0074] The OH number and viscosity values ​​given above were determined for 100% material. The oxide unit values ​​given are based on the whole molecule. To arrive at the values ​​for a, b, and c from the above numbers, these must be divided by the number of active hydrogen atoms in the starting material molecule, e.g., 3 for glycerin, 4 for pentaerythritol.

[0075] [Table 2] TIFF0007762067000005.tif233170

[0076] To evaluate the suitability of the polymers as dispersants for pigments, aqueous pigment pastes were prepared. For this purpose, the pigments were pasteified in deionized water together with the dispersants according to the invention and other additives known from the prior art, and then predispersed in a dissolver (e.g., CN-F2 type from VMA-Getzmann GmbH) or other suitable equipment. Subsequently, fine dispersion was carried out using a bead mill (e.g., APS 500 from VMA-Getzmann) or other suitable dispersing equipment, where grinding was carried out under cooling using silica zite beads or zirconium mixed oxide beads with a size of d = 1 mm. Subsequently, the grinding media were separated from the pigment dispersion, and the latter was evaluated. In particular, the polymers according to the invention were compared with comparative samples with regard to viscosity, tinting strength, and compatibility.

[0077] For this purpose, the following four base formulations were selected (all figures given in % by weight based on total composition = 100%):

[0078] [Table 3]

[0079] To produce the pigment preparation, components B, C, D, E, F, and G were introduced and mixed. Powdered component A was then added and pre-dispersed using a dissolver. Fine dispersion was carried out in a bead mill with zirconium mixed oxide beads of d = 1 mm while cooling. The milling time was 30-60 minutes. The milling media was then separated and the pigment preparation isolated. After 24 hours, the pigment preparation was tested for tinting strength (coloring in emulsion paint) and viscosity. It was then stored at 50°C for 28 days and re-tested for the two aforementioned properties, which indicates its storage stability.

[0080] The viscosity was measured using a Thermofischer GmbH cone-plate viscometer (Haake Viskostester 550 model) at 20°C from 0 to 200 s. -1The shear rate range was tested at 60 s -1 A shear rate of 1000 rpm was used to indicate viscosity.

[0081] Storage stability was assessed based on viscosity. Storage stability after 24 hours was compared to the viscosity measured after 28 days of heated storage at 50°C. Pastes were assessed as "very good" storage stable if their viscosities did not differ by more than 200 mPas and the pastes did not exhibit settling or syneresis. Storage stability was assessed as "good" if the viscosity changed by more than 200 mPas and / or slight settling occurred. Pastes that were not storage stable thickened significantly during storage (viscosity increase of more than 400 mPas) or became solid or thixotropic.

[0082] The tinting strength was determined according to DIN 55986 by tinting an emulsion paint at 2% with the paste of interest. The tinted paint was then applied to a paint card in the specified layer thickness and, after drying, examined in a Konica Minolta spectrophotometer.

[0083] Compatibility was determined by a rub-out test. For this purpose, the emulsion paint was mixed with the pigment dispersion and then applied to a paint card. The bottom of the paint card was subsequently rubbed with a finger. If the rubbed surface was more pigmented than the adjacent untreated surface, then incompatibility was observed (see also DE 2368946). The following results were obtained:

[0084] [Table 4]

[0085] As can be seen from the above examples, better results are achieved in terms of tinting strength, compatibility, viscosity and storage stability when polyols are used as starting materials and the amounts of oxirane derivatives according to the invention are used.

[0086] The Pigment Blue 15:3 used in the formulation of Example A can be satisfactorily dispersed in all cases using Samples 1 to 3 according to the invention. In contrast, the formulations using Comparative Samples 1 and 2 are not storage-stable, and Comparative Sample 1 exhibits a significant increase in viscosity and thixotropy during storage. On the other hand, Comparative Samples 3 and 4, which do not contain styrene oxide or ethylene oxide according to the invention, exhibit very strong foaming. Furthermore, the formulation using Comparative Sample 3 is already semi-solid after one week. The formulation using Comparative Sample 4 is also not storage-stable.

[0087] Pigment Yellow 74, used in all formulations of Example B, is a pigment that can be dispersed relatively easily and therefore satisfactorily with many dispersant samples. Comparative Sample 2 exhibits very strong rub-out, indicating a strong incompatibility between the paste and the base paint. Comparative Sample 1 results in a pigment preparation containing volatile organic components (VOC / SVOC). Furthermore, Comparative Samples 3 and 4 are notable for their strong foaming and lack of storage stability.

[0088] Pigment Green 7 used in the formulation of Example B can be satisfactorily dispersed in all aspects using Samples 1 to 3 of the present invention. On the other hand, Comparative Sample 1 exhibits defects of lack of storage stability, including thixotropy and a viscosity increase of more than 1000 mPas within one week. Comparative Sample 2 again exhibits a strong incompatibility defect, as very strong rub-out is observed.

[0089] Pigment Red 101 is the only example of an inorganic pigment. Sample 1 is also able to disperse this inorganic pigment sufficiently well. A slight settling occurs during storage, but this can be easily re-stirred. In longer-term preparations, this property can be re-compensated with rheological additives. Comparative Sample 1 was unable to produce a flowable paste.

[0090] Comparative Sample 1 starts with ethylenediamine and contains diglyme as a VOC / SVOC contributing solvent. With this dispersant, similarly good tinting strength can be achieved with organic pigments as with Samples 1-3 according to the invention, but only pastes with the less demanding Pigment Yellow 74 are storage stable. Comparative Sample 1 is not recommended for red iron oxide.

[0091] Comparative Sample 2 also contains ethylenediamine as the starting material, but also contains one unit of propylene oxide per active amine oxygen before the styrene oxide block. This synthesis strategy allows for solvent-free operation, since the single propoxylation increases the molecular weight of the starting material. Therefore, the requirement for a VOC / SVOC-free dispersant is met. However, Comparative Sample 2 often results in incompatibility with the base paint during pigmentation, which is evident by a strong rub-out of yellow and green colors.

[0092] In the case of Pigment Blue 15:3, the paste was not storage stable and a strong precipitate formed that could not be easily redissolved. Therefore, this sample does not meet the requirements.

[0093] The amine-initiated comparative samples fail to meet the requirements in all claims and in all tested pigment preparations: they do not have formula (I) or (II) according to the invention as starting materials.

[0094] Also, comparative sample 3, which has a styrene oxide proportion (a=1) not according to the invention, does not fulfill the objectives, nor does comparative sample 4, which has an ethylene oxide proportion that is too high (c=35).

[0095] Samples 1-3 according to the invention solve the technical problem posed with respect to pigment dispersions, regardless of whether propoxylation was carried out on the polyol starting material (Sample 1) or not (Samples 2-3).

[0096] In summary, it can be said that this task can only be achieved by the polymers according to the invention, which have a polyol starting material and the appropriate proportions of styrene oxide and ethylene oxide, and which only meet all the necessary criteria in the resulting pigment preparation.

[0097] Examples of plant protection formulations

[0098] [Table 5]

[0099] In the crop protection formulations with tebuconazole, only the formulation with sample 2 according to the invention gives a stable suspension, whereas the formulation with the comparative sample gives a solid. The present application relates to the invention described in the claims, but may also include the following as other aspects. (1) Compositions containing compounds of formula (I), formula (II), or mixtures thereof [ka] [In the formula, n is an integer equal to or greater than 1, R 1 is an aliphatic linear or branched hydrocarbon residue having 1 to 10 carbon atoms, a hydrogen atom, a structural unit -OX, or a structural unit -CH 2 -OX, X corresponds to formula (III) [ka] (In the formula, a is an integer from 2 to 6, b is an integer from 0 to 3, c is an integer from 20 to 28; m is 1 or 2; R 2 is an aliphatic linear or branched hydrocarbon residue having 1 to 10 carbon atoms, Y is hydrogen, -SO 3 M, -SO 2 M, -PO 3 M 2 or -CH 2 COOM, and M is a cation). (2) The composition according to (1) above, wherein in formula III, viewed from the left, block m precedes block c, and blocks a and b are arranged within m, either randomly or in a block manner. (3) The composition according to (1) or (2) above, wherein a is 3, 4 or 5, particularly 3 or 4. (4) The composition according to any one of the above (1) to (3), wherein b is an integer of 0 to 2, particularly 0 or 1. (5) The composition according to any one of (1) to (4) above, wherein m is 1. (6) Y is H or -PO 3 M 2 The composition according to any one of (1) to (5) above, (7) The composition according to any one of (1) to (6) above, wherein the ratio of (a+b):c is 1:4 to 1:6. (8). a represents a number from 2 to 6, in particular 3, 4 or 5; b represents a number from 0 to 3, c represents the numbers 20 to 28, m represents 1 or 2, and Y is H or -PO 3 M 2 Represents, The composition according to any one of (1) to (7) above. (9) The composition according to any one of (1) to (7) above, wherein a is a number from 2 to 6, b is 0 or 1, m is 1, and c is a number from 20 to 28. (10).R 1 Ga-CH 2 The composition according to any one of (1) to (9) above, wherein the compound represents —OX. (11).R 2 Ga-CH 3 The composition according to any one of the above (1) to (9), wherein (12) The composition according to any one of the above (1) to (9), wherein n represents 1. (13) A compound of formula (I), formula (II), or a mixture thereof

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Claims

1. Dispersants or emulsifiers containing compounds of formula (I), formula (II) or mixtures thereof 【Chemistry 1】 [In the formula, n is 1, R １ is the structural unit -CH ２ -O-X, X corresponds to formula (III) 【Chemistry 2】 (In the formula, a is an integer from 2 to 6, b is an integer from 0 to 3; c is an integer from 20 to 28; m is 1 or 2; R ２ is -CH ３ and Y is hydrogen or -PO ３ M ２ and M is hydrogen, Na ＋ , K. ＋ , N.H. ４ ＋ , triethanolammonium, or a combination thereof; and From the left, block m precedes block c, and blocks a and b are arranged within m, either randomly or in a block fashion).

2. 2. The dispersant or emulsifier of claim 1, wherein a is 3, 4, or 5.

3. 3. A dispersant or emulsifier according to claim 1 or 2, wherein b is an integer from 0 to 2.

4. A dispersant or emulsifier according to any one of claims 1 to 3, wherein m is 1.

5. A dispersant or emulsifier according to any one of claims 1 to 4, wherein the ratio of (a+b):c is from 1:4 to 1:

6.

6. 2. The dispersant or emulsifier of claim 1, wherein a is a number from 2 to 6, b is 0 or 1, m is 1, and c is a number from 20 to 28.

7. Use of compounds of formula (I), formula (II) or mixtures thereof as dispersants for aqueous formulations of plant protection agents 【Transformation 3】 [In the formula, n is 1, R １ is the structural unit -CH ２ -O-X, X corresponds to formula (III) 【Chemistry 4】 (In the formula, a is an integer from 2 to 6, b is an integer from 0 to 3; c is an integer from 20 to 28; m is 1 or 2; R ２ is -CH ３ and Y is hydrogen or -PO ３ M ２ and M is hydrogen, Na ＋ , K. ＋ , N.H. ４ ＋ , triethanolammonium, or a combination thereof; and From the left, block m precedes block c, and blocks a and b are arranged within m, either randomly or in a block fashion).

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