EP1942729A1

EP1942729A1 - Solid formulations containing polyalkoxylate, method for their production and use thereof

Info

Publication number: EP1942729A1
Application number: EP06807634A
Authority: EP
Inventors: Reiner Kober; Reinhold Stadler; Karl-Heinrich Schneider; Michael SCHÖNHERR
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-10-28
Filing date: 2006-10-27
Publication date: 2008-07-16
Also published as: CN101351119A; JP2009513609A; WO2007048850A1; JP5479736B2; TW200724603A; US20090131260A1; AR058822A1; BRPI0618033A2; DE102005051830A1; UY29888A1

Abstract

The invention relates to solid formulations comprising: a) a liquid or low-melting polyalkoxylate and b) a carrier based on high-molecular sulfonate. According to the invention: (i) the fraction of liquid or low-melting polyalkoxylate (in relation to the total weight of the solid formulation) constitutes at least 15 % by weight; (ii) the fraction of liquid or low-melting polyalkoxylate (in relation to the total weight of the high-molecular sulfonate) constitutes at least 30 % by weight; (iii) the maximum weight ratio of liquid or low-melting polyalkoxylate to high-molecular sulfonate is 3:1. The invention also relates to the use of said formulations, in particular in the field of crop protection and to a method for producing formulations of this type.

Description

Polyalkoxylate-containing solid formulations, process for their preparation and their use

The invention relates to solid formulations with liquid or low-melting polyalkoxylates, their use in particular in the field of crop protection and to processes for producing such formulations.

Year by year, a considerable part of agricultural production worldwide is destroyed by plant pests in the broadest sense. Plant pests can not only lead to crop failures on a large scale, endangering human nutrition, but also destroy the vegetative parts of perennial crops, sustainably disrupting agricultural land and entire ecosystems.

Plant pests belong to different groups of organisms. Among higher animals, insects and mites in particular contain numerous important pests, as well as nematodes and snails; Vertebrates such as mammals and birds are of lesser importance in industrialized countries today. Many groups of microbes, including fungi, bacteria including mycoplasmas, viruses and viroids, can cause crop failure and loss of value; Even basically edible products are often no longer available for aesthetic reasons.

Finally, weeds, which compete with crops for scarce habitat and other resources, are also pests in the wider sense.

Parasitic fungi are of particular importance as pests. Mildew is feared in horticulture, ergot (Claviceps) endangers humans and animals by its toxic alkaloids, and historical damage to the European potato stocks by Phytophthora infestans in the mid-19th century, which led to famine and political unrest.

Under the generic term "plant protection products" substances and mixtures of substances are summarized, which can be used for the specific control of plant pests.They can be divided into target organisms (insecticides, fungicides, herbicides, etc.), by type of action (edible toxins, contact poisons, quenching agents, etc.) or chemical In particular, against phytopathogenic fungi, because of the resistance of the fungal spores and the absence of natural enemies, chemical control is the only effective measure to be taken To maximize the effect of the fungicides locally, so as not to harm symbiotic fungi (mycorrhizal fungi) in other places.

Plant protection products can be pure substances, but compositions are advantageous in many cases. Such compositions may contain, in addition to or directly to the pests acting substance or substances (hereinafter referred to as crop protection agent) different types of accompanying and auxiliary substances that enhance the desired effect in different ways (in the literature then mostly "additives", "Adjuvants", "accelerators", "boosters" or "enhancers" called), simplify the handling, increase the shelf life or otherwise improve the properties of the product.

Typically, pesticides are dissolved, emulsified or dispersed in an aqueous medium so as to obtain the aqueous spray mixture referred to as "tank mix", which is then applied to the plants or their habitat by the so-called spraying method to get a suitable tank mix.

The effect of effect-promoting additives is generally based on their interfacial activity against the hydrophobic plant surface, which is the contact of the

Spray mixture with the plant surface improved. In detail, a distinction is made between wetting agents, spreaders, and permeabilizers ("penetrators"), which naturally overlap.The general term additive, without taking physical details into account, is used to designate auxiliary agents to increase the activity of agro-technical agents, in particular pesticides used.

Nonionic, hydrophobic alkoxylates are known as suitable additives for various crop protection agents, especially fungicides.

Such alkoxylates are used primarily in liquid formulations, which include solutions, emulsions, suspensions, suspoemulsions and other forms. For example, EP 707445 B1 shows relatively stable suspoemulsions.

However, liquid formulations have a number of disadvantages: In the application there is a risk of leakage and seepage in the ground. Storage and Transport is more complicated because the solvent must be transported along or be stored, and containers for liquid formulations - such as containers or canisters - cause disposal problems, since a simple combustion is generally not possible. The stability of liquid formulations against heat, cold and shear forces and thus their storage stability is low and requires expensive emulsifier and stabilizer additives. In addition, many active substances or combinations of active ingredients can only be formulated poorly in liquid form, since they tend to crystallize and / or segregate. The solvents themselves are often highly flammable, irritating to the skin or unpleasant odor; If water is used as a solvent, the problem of hydrolytic degradation of active substances often arises during prolonged storage.

Solid state formulations, in particular non-dusty solid granules, offer considerable advantages over liquid formulations in terms of application, storage, transport, stability and disposal of packaging. Often disadvantageous, however, is the low melting temperature of the abovementioned alkoxylates, which leads to problems when incorporated into solid formulations. Thus, conventional solid formulations can only absorb small amounts of liquid, oil-like or low-melting additives, such as the alkoxylates, since otherwise the gluing and clumping of the granules result. Typically, without affecting storage stability, only less than 15% by weight of such additives can be added.

The proportion of additives which can be used can traditionally be increased by the use of sorbents, also called "carriers", based on mineral, especially silicate-based, additives which improve the mechanical properties of the composition and prevent the granules from clumping during the process However, mineral sorbents have a tendency to form very fine-grained powders and dusts, which in turn causes problems during production and processing and in particular requires complex safety technology, especially in the field of respiratory protection in that the solid constituents can also develop undesired effects after application. No. 6,239,115 B1 describes granules with the active ingredient polyoxin and naphthalenesulfonic acid-formaldehyde condensates as dispersants. Here, however, typically only 2% of polyoxyethylene alkyl ethers were incorporated into the granules.

DE 102 17 201 describes low-dust granules with up to 9% of alkyl sulfonates and / or polyglycols. The polyglycols are generally not suitable enhancers because they are purely water-soluble and not surface-active.

GB 1291251 describes granules with only up to 5% of anionic and nonionic surfactants, but up to 50% of calcium lignosulfonates.

The incorporation of surface-active and effect-enhancing aids can, for. For example, WO 93/25074 provides, with virtually no exception, Carbowax (PEG 8000) being used as a so-called "binder". PEGs, d. H. Polyethylene glycols, are generally very hydrophilic, so very good water-soluble.

EP 843 964 B1 essentially describes extrusion granules with up to 10% of tristyrylphenyl polyethoxylates, mineral carrier systems ("carriers") being used as in US Pat. No. 6,416,775 B1, for example US Pat. No. 6,416,775 B1 or US Pat B1 diatomaceous earth (diatomaceous earth), in particular Celite products, used as sorbing agents.

DE 696 24 381 T2, WO 97/24173 or EP 880 402 B1 describe granules of ligninsulfonates with relatively small proportions of di- and tristyrylphenol ethoxylates.

One way to produce granules with high levels of liquid amphiphilic surface-active additives describe, for. WO 99/56543 and WO 99/08518. Here, so-called clathrates from urea derivatives and polysiloxane-derivatized alcohol ethoxylates are described. This should allow powder or granules to be produced with up to 30% of surface-active auxiliaries.

According to WO 93/05652 a solution for the production of herbicidal granules with so-called activators is shown. If fatty alcohol ethoxylates are used, then in the granules high levels of mineral sorbents or carriers based on silicate. The latter have the above-mentioned disadvantages.

In summary, it can be said that the state of the art does not show any possibility of incorporating high levels of liquid or low-melting additives into solid formulations without having to resort to mineral carrier systems. It was therefore the object to provide solid formulations with high levels of such additives available.

Surprisingly, it has now been found that liquid or low-melting polyalkoxylates, combined in suitable amounts with relatively high molecular weight sulfonates, are capable of yielding advantageous solids formulations, in particular granules.

An object of the present invention is therefore a solid formulation comprising: a) liquid or low melting polyalkoxylate; and b) a carrier based on high molecular weight sulfonate, wherein

(i) the proportion of liquid or low melting polyalkoxylate relative to the total weight of the solid formulation is at least 15% by weight;

(ii) the proportion of liquid or low melting polyalkoxylate based on the total weight of the higher molecular weight sulphonate is at least 30% by weight;

(iii) the weight ratio of liquid or low melting polyalkoxylate to higher molecular weight sulfonate is at most 3: 1.

The solid formulation according to the invention therefore basically comprises two components:

(a) a polyalkoxylate component which is liquid or low melting by itself and consists of a polyalkoxylate or a mixture of several polyalkoxylates; and

(b) an inherently solid support component comprising one or more higher molecular weight sulfonates. Here, the proportion of liquid or low melting polyalkoxylate is at least 15 wt .-%, based on the total weight of the solid formulation, and at least 30%, based on the total weight of the higher molecular weight sulfonates. The proportion of liquid or low-melting polyalkoxylate may also be greater than the proportion of higher molecular weight sulphonate, but at most up to a weight ratio of 3: 1. The carrier component (b) generally comprises predominantly higher molecular weight sulfonate.

The term "liquid" refers to the liquid state of matter at normal pressure and a temperature in the range from 20 to 30 ° C. A low-melting polyalkoxylate generally has a melting point of less than 40 ° C., in particular less than 30 ° C.

According to a particular embodiment, the polyalkoxylate to be used is olefinic. Herein, the term "oleaginous" refers to a viscous, sticky-greasy physical consistency; chemically, the substance may be lipophilic, hydrophilic or amphiphilic. "Generally, the polyalkoxylates are amphiphilic.

The polyalkoxylates according to the invention basically comprise a hydrophobic or lipophilic part and one or more polymeric alkoxylate parts (polyalkoxylate or macrogol parts), the or each individual polyalkoxylate part being linked for example via an amide, ether or ester bond with the hydrophobic or lipophilic part is linked. In this case, "polymer" means at least two, in particular at least three, more particularly from 3 to 1000, low molecular weight units. These units may either be identical to one another to give a monotone polymer or at least two different alkylene oxide types In the latter case, it is preferable to each block a plurality of alkylene oxide units of one type so that the structural elements of the polymer are at least two different alkylene oxide blocks, each of which consists of a monotonic series of identical alkylene oxide units (block polymer or block copolymer If such block alkoxylates are used, it is preferred that the alkylene oxide part be composed of 2 or 3 and in particular of 2 blocks If the polyalkoxylate part comprises different blocks, the parts closer to the hydrophobic or lipophilic part than "proximal" which are more distant than " distal "and the terminal referred to as" terminal ". As AI according to the invention Examples of alkoxylate monomers include ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), pentylene oxide (PeO) and hexylene oxide (HO).

Particular polyalkoxylates can be found among the alkoxylated fatty alcohols, alkoxylated fatty acid esters, alkoxylated fatty amines, alkoxylated glycerides, alkoxylated sorbitan esters, alkoxylated alkylphenols and alkoxylated di- and tristyrylphenyls, the alkylphenols preferably being alkylated several times, in particular twice or three times. Furthermore, the polyalkoxylates may also be end-group modified, i. the terminal OH group of the alkoxylate part is modified, for example etherified or esterified. Suitable end-group-modified polyalkoxylates include in particular alkylated, alkenylated or arylated polyalkoxylates, preferably those having a methyl or tert-butyl group or a phenyl group, or polyalkoxylate esters, e.g. Mono- or diphosphate esters or sulfate esters, and their salts, for example the alkali metal or alkaline earth metal salts. Such end group modification can be carried out for example with dialkyl sulfate, Ci_io-alkyl halide or phenyl halide.

At least part of the alcohol polyalkoxylates to be used is known per se. For example, WO 01/77276 and US Pat. No. 6,057,284 and EP 0 906 150 describe suitable alcohol polyalkoxylates. The description of these alcohol polyalkoxylates in these publications is hereby incorporated by reference, whereby the alcohol polyalkoxylates disclosed therein and also their preparation are part of the present disclosure.

In a further particular embodiment, alcohol polyalkoxylates are present under alcohol polyalkoxylates according to the formula (I)

R ⁷ -O- (C _m H _2m O) _x - (C _n H _2n O) _y - (C _p H _2p O) _z -R ⁶ (I)

selected in which

R ^{6 is} an organic radical;

R ^{7 is} an aliphatic hydrocarbon radical having 3 to 100 carbon atoms; m, n, p are independently an integer from 2 to 6, preferably from 2, 3, 4 or 5;

x, y, z independently represent a number from 0 to 1000; and

x + y + z corresponds to a value of 2 to 1000.

The aliphatic hydrocarbon radical (R ⁷ ) is usually hydrophobic or lipophilic, whereby the alcohol polyalkoxylates get their oil-like properties. In particular, R ^{7 is} a branched or linear hydrocarbon radical having 3 to 30 and preferably 5 to 24 carbon atoms, which may be saturated (in particular C ₃ _ ₃ o-alkyl) or unsaturated (in particular C _3-3 o-alkenyl).

The organic radical (R ⁶ ) typically contributes less than 10% and preferably less than 5% to the molecular weight of the alcohol polyalkoxylate of the formula (I) and is preferably hydrogen, alkyl, preferably C 1-10 -alkyl, more preferably methyl or tert-butyl, alkenyl, preferably C ₂ -alkenyl, acyl, in particular acetyl, propionyl, butyryl or benzyl, aryl, in particular phenyl, or for an inorganic acid group, in particular phosphate, diphosphate or sulfate.

According to one aspect, it is preferred that the alcohol polyalkoxylates to be used according to the invention are ethoxylated or have at least one ethylene oxide block. In another aspect, ethylene oxide blocks are combined in particular with propylene oxide or pentylene oxide blocks.

In a particular embodiment, alcohol polyalkoxylates of formula (I) are used wherein m = 2 and x> 0. These are alcohol polyalkoxylates of the EO type, which include, in particular, alcohol ethoxylates (m = 2, x> 0; y, z = 0) and alcohol polyalkoxylates having a proximal EO block (m = 2, x> 0; y and / or z> 0).

Yet another particular embodiment of the alcohol polyalkoxylates with a proximal EO block represent those with a terminal block of other monomers (n>2;y> 0). Among these, especially EO-PO block alkoxylates (n = 3, y> 0, z = 0) may be mentioned. Preference is given to EO-PO block alkoxylates in which the ratio of EO to PO (x to y) is preferably 1: 1 to 4: 1 and in particular 1: 5: 1 to 3: 1. The degree of ethoxylation (value of x) is generally 1 to 20, preferably 2 to 15 and in particular 4 to 10, the degree of propoxylation (value of y) is generally 1 to 20, preferably 1 to 8 and in particular 2 to 5. The total degree of alkoxylation, ie the sum of EO and PO units, is generally 2 to 40, preferably 3 to 25 and in particular 6 to 15.

Among the particularly preferred alcohol polyalkoxylates having a proximal EO block, mention may also be made of EO-PeO block alkoxylates (n = 5, y> 0, z = 0). Preference is given here to EO-PeO block alkoxylates in which the ratio of EO to PeO (x to y) is preferably 2: 1 to 25: 1 and in particular 4: 1 to 15: 1. The degree of ethoxylation (value of x) is generally 1 to 50, preferably 4 to 25 and in particular 6 to 15, the degree of pentoxylation (value of y) is generally 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2. The Gesamtalkoxylierungsgrad, ie the sum of EO and PeO units is generally 1.5 to 70, preferably 4.5 to 29 and in particular 6.5 to 17.

According to a further particular embodiment, alcohol polyalkoxylates of the formula (I) are used in which n = 2, the values of m, x and y are each greater than zero and z = 0. Again, these are EO-type alcohol polyalkoxylates in which the EO block is bound distally and another polyalkoxylate block is interposed between it and the alkyl moiety. These include, in particular, PO-EO block alkoxylates and PeO-EO block alkoxylates (n = 2, x> 0, y> 0, m = 5, z = 0).

Yet another particular embodiment of such alcohol polyalkoxylates with distal EO block are PO-EO block alkoxylates (n = 2, x> 0, y> 0, m = 3, z = 0) in which the ratio of PO to EO (x to y) preferably 1: 10 to 3: 1 and in particular 1, 5: 1 to 1: 6. The degree of ethoxylation (value of y) is generally 1 to 20, preferably 2 to 15 and in particular 4 to 10, the degree of propoxylation (value of x) is generally 0.5 to 10, preferably 0.5 to 6 and in particular 1 to 4. The Gesamtalkoxylierungsgrad, ie the sum of EO and PO units is usually 1, 5 to 30, preferably 2.5 to 21 and especially 5 to 14.

In another particular embodiment, alcohol polyalkoxylates of formula (I) are used wherein m = 5 and x> 0. These are alcohol polyalkoxylates of the PeO type. Particularly preferred are PeO-EO block alkoxylates (n = 2, y> 0, z = 0) in which the ratio of PeO to EO (x to y) is 1:50 to 1: 3 and especially 1: 25 to 1: 5. The degree of pentoxylation (value of x) is generally 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2, the degree of ethoxylation (value of y) is usually 3 to 50, preferably 4 to 25 and in particular 5 to 15. The Gesamtalkoxylierungsgrad, ie the sum of EO and PeO units is usually 3.5 to 70, preferably 4.5 to 45 and in particular 5.5 to 17.

According to a particular embodiment, the alcohol polyalkoxylates are not end-group-modified, ie R ⁶ is hydrogen.

According to a preferred embodiment of the invention, the alcohol moiety of the alcohol polyalkoxylates is based on known alcohols or alcohol mixtures having 5 to 30, preferably 8 to 20 and in particular 9 to 15 carbon atoms. In particular, fatty alcohols having about 8 to 20 carbon atoms may be mentioned here. Many of these fatty alcohols are known to be used for the preparation of nonionic and anionic surfactants, for which the alcohols of a corresponding functionalization, e.g. by alkoxylation or glycosidation.

The alcohol part can be straight-chain, branched or cyclic. If it is linear, alcohols having 14 to 20, for example, 16 to 18 carbon atoms are to be mentioned in particular. If it is branched, according to a particular embodiment, the main chain of the alcohol part generally has 1 to 4 branches, it also being possible to use alcohols having a higher or lower degree of branching in a mixture with other alcohol alkoxylates, as long as the average number of branches of the mixture is in the specified range.

The alcohol part can be saturated or unsaturated. If it is unsaturated, it has, according to a particular embodiment, a double bond. In general, the branches of the alcohol moiety independently of one another each have 1 to 10, preferably 1 to 6 and in particular 1 to 4, carbon atoms. Particular branches are methyl, ethyl, n-propyl or isopropyl groups.

Suitable alcohols and in particular fatty alcohols are both from natural sources, for example by recovery and required or if desired, by hydrolysis, transesterification and / or hydrogenation of glycerides and fatty acids, as well as by a synthetic route, for. B. by construction of educts with a lower number of carbon Atoms available. So you get z. For example, according to the SHOP process (Shell Higher Olefinic Process) starting from ethene olefin fractions with a carbon number suitable for further processing into surfactants. The functionalization of the olefins to the corresponding alcohols takes place z. By hydroformylation and hydrogenation.

The alkoxylation results from the reaction with suitable alkylene oxides. Depending on the chosen for the reaction amounts of alkylene oxide (s) and the reaction conditions, the respective degree of alkoxylation results. This is usually a statistical average as the number of alkylene oxide units of the alcohol polyalkoxylates resulting from the reaction varies.

The degree of alkoxylation, i. the average chain length of the polyether chains to be used according to the invention alcohol polyalkoxylates can be bestimmmt by the molar ratio of alcohol to alkylene oxide. Alcohol polyalkoxylates having from about 2 to 100, preferably from about 2 to 50, in particular from 3 to 30, especially from 4 to 20 and especially from 5 to 15, alkylene oxide units are preferred.

The reaction of the alcohols or alcohol mixtures with the alkylene oxide (s) is carried out by customary methods known to the person skilled in the art and in apparatuses customary for this purpose.

The alkoxylation reaction can be catalyzed by strong bases such as alkali hydroxides and alkaline earth hydroxides, Brönsted acids or Lewis acids such as AICI ₃ , BF _3, etc. For narrow alcohol alkoxylates, catalysts such as hydrotalcite or DMC can be used.

The alkoxylation is preferably carried out at temperatures in the range of about 80 to 250 ° C, preferably about 100 to 220 ° C. The pressure is preferably between ambient pressure and 600 bar. If desired, the alkylene oxide may be an inert gas admixture, e.g. From about 5 to 60%.

According to a preferred embodiment, the alcohol polyalkoxylates to be used according to the invention are based on primary, α-branched alcohols of the formula (IV)

wherein

R ¹⁰ , R ^{11 are} independently hydrogen or dC ₂₆ alkyl.

Preferably, R ¹⁰ and R ¹¹ independently of one another are C ₁ -C ₆ -alkyl and in particular C ₂ -C ₄ -alkyl.

According to a particular embodiment, alcohol polyalkoxylates are used whose alcohol part is 2-propylheptanol. These include, in particular, alcohol polyalkoxylates of the formula (I) in which R ^{7 is} a 2-propylheptyl radical, ie R ¹⁰ and R ¹¹ in formula (IV) are each n-propyl.

Such alcohols are also referred to as Guerbet alcohols. These can be obtained, for example, by dimerization of corresponding primary alcohols (eg R ^{10 11} -CH ₂ CH ₂ OH) at elevated temperature, for example 180 to 300 ° C., in the presence of an alkaline condensing agent such as potassium hydroxide. In the context of this preferred embodiment based on Guebert alcohols, especially EO-type alkoxylates are used. Particular preference is given to ethoxylates whose degree of ethoxylation is 2 to 50, preferably 2 to 20 and in particular about 3 to 10. Of these, especially the corresponding ethoxylated 2-propylheptanols should be mentioned.

According to a further particular embodiment, alcohol polyalkoxylates are used whose alcohol part is a C ₃ -oxo-alcohol.

It is particularly preferred if these oxoalcohols Ci ₃ ₂ hydrocarbons are obtainable by hydroformylation and subsequent hydrogenation of unsaturated Ci, in particular by hydrogenation of hydroformylated trimeric butene or by hydrogenation of hydroformylated dimeric hexene.

The term "C ₃ oxo alcohol" usually referred to an alcohol mixture whose main component of at least one branched Ci3 alcohol (isotridecanol) Sex is formed. Such alcohols include, in particular Ci ₃ tetramethylnonanols, for example, 2,4,6,8-tetramethyl-1-nonanol or 3,4,6,8-tetramethyl-1-nonanol and furthermore Ethyldimethylnonanols such as 5-ethyl-4,7- dimethyl-1-nonanol.

Suitable C 13 -alcohol mixtures are generally obtainable by hydrogenation of hydroformylated trimerbutene. In particular, you can

1) for the oligomerization of butenes with a suitable catalyst contacting, 2) from the reaction mixture a C ₂ -olefin isolate

3) hydroformylating the Ci ₂ -Olefinfraktion by reaction with carbon monoxide and hydrogen in the presence of a suitable catalyst, and

4) hydrogenate.

The buttrimerization preceding hydrogenation may be by homogeneous or heterogeneous catalysis.

From the reaction of oligomerization reaction described initially is then suitable for presentation C ₁₃ is in one or more separation steps - alcohol mixtures by hydroformylation and hydrogenation of suitable C ₂ olefin fraction isolated (step 2). Suitable separation devices are the usual apparatuses known to the person skilled in the art.

For the preparation of an alcohol mixture according to the invention so isolated is C ₁₂ - to C ₃ olefin fraction is hydroformylated aldehydes (process step 3) and then to C ₃ alcohols hydrogenated (step 4). The preparation of the alcohol mixtures can be carried out in one stage or in two separate reaction steps.

For a review of hydroformylation processes and suitable catalysts, see Beller et al., Journal of Molecular Catalysis A 104 (1995), p. 17-85.

For hydrogenation, the reaction mixtures obtained in the hydroformylation are reacted with hydrogen in the presence of a hydrogenation catalyst.

Other suitable C _1-3 -alcohol mixtures are obtainable by reacting 1) subjects a C ₄ olefin mixture to metathesis,

2) separates from the metathesis mixture olefins having 6 C atoms,

3) subjecting the separated olefins, individually or in a mixture of dimerization, to olefin mixtures having 12 C atoms, and 4) subjecting the resulting olefin mixture, optionally after fractionation, to derivatization to a mixture of C ₃ -oxoalcohols.

From the mixture obtained after the hydrogenation, the inventive Ci ₃ -alcohol mixture for use as component (a) can be obtained pure by conventional, known in the art purification process, in particular by fractional distillation.

C 13 -alcohol mixtures according to the invention generally have a mean degree of branching of from 1 to 4, preferably from 2.0 to 2.5 and in particular from 2.1 to 2.3 (based on trimerbutene) or from 1, 3 to 1, 8 and in particular 1, 4 to 1, 6 (on

Base of dimer hexene). The degree of branching is defined as the number of methyl groups in a molecule of the alcohol minus 1. The mean degree of branching is the statistical mean of the degrees of branching of the molecules of a sample. The average number of methyl groups in the molecules of a sample can easily be determined by ¹ H NMR spectroscopy. For this, the signal area corresponding to the methyl protons in the 1 H-NMR spectrum of a sample is divided by 3 and related to the divided by two signal surface of the methylene protons in the CH ₂ -OH group.

In the context of this particular embodiment on the basis of C ₃ -oxo in particular, those are preferred alcohol alkoxylates are ethoxylated or are block either the EO / PO type.

The degree of ethoxylation of the present invention to be used ethoxylated C ₁ 3- oxo alcohols is generally from 1 to 50, preferably 3 to 20 and especially 3 to 10, especially 4 to 10 and preferably 5 to 10 degrees.

The degrees of alkoxylation of the EO / PO block alkoxides to be used according to the invention depend on the arrangement of the blocks. If the PO blocks are arranged terminally, the ratio of EO units to PO units is generally at least 1, preferably 1: 1 to 4: 1 and in particular 1: 5: 1 to 3: 1. The degree of ethoxylation is generally 1 to 20, preferably 2 to 15 and especially 4 to 10, the degree of propoxylation is usually 1 to 20, preferably 1 to 8 and especially 2 to 5. The Gesamtalkoxylierungsgrad, ie the sum of EO and PO units is usually 2 to 40, preferably 3 to 25 and especially 6 to 15. If the EO blocks, however, arranged terminal, the ratio of PO blocks to EO blocks is less critical and is usually 1:10 to 3: 1, preferably 1: 1, 5 to 1: 6. The degree of ethoxylation is generally 1 to 20, preferably 2 to 15 and in particular 4 to 10, the degree of propoxylation is usually 0.5 to 10, preferably 0.5 to 6 and in particular 1 to 4. The Gesamtalkoxylierungsgrad is usually 1.5 to 30, preferably 2.5 to 21 and especially 5 to 14.

According to a further particular embodiment, alcohol polyalkoxylates are used whose alcohol part is a Cio-oxo-alcohol. The term "Cio-oxo-alcohol" is analogous to the above-mentioned term "C ₁₃ -oxo alcohol" for Cio-alcohol mixtures whose main component is formed from at least one branched Cio-alcohol (isodecanol).

It is particularly preferred if suitable C ₀ can be obtained by hydrogenation of hydroformylated trimeric propene alcohol mixtures.

In particular, you can

1) bringing propenes into contact with a suitable catalyst for the purpose of oligomerization,

2) from the reaction mixture to isolate a Cg-olefin fraction, 3) the Cg-olefin fraction by reaction with carbon monoxide and hydrogen in

Hydroformylate the presence of a suitable catalyst and 4) hydrogenate.

Particular embodiments of this procedure are analogous to the embodiments described above for the hydrogenation of hydroformylated trimer butene.

In the context of this embodiment based on Cio-oxo alcohols, particular preference is given to those alcohol polyalkoxylates which are either ethoxylated or block oxylates of the EO / PeO type. The degree of ethoxylation of the present invention to be used ethoxylated Ci ₀ - oxo alcohols is generally from 2 to 50, preferably 2 to 20 and especially 2 to 10, especially 3 to 10 and especially 3 to 10.

The degrees of alkoxylation of the EO / PeO block alkoxylates to be used according to the invention depend on the arrangement of the blocks. If the PeO blocks are arranged terminally, then the ratio of EO units to PeO units is generally at least 1, preferably 2: 1 to 25: 1 and in particular 4: 1 to 15: 1. The degree of ethoxylation is generally 1 to 50, preferably 4 to 25 and especially 6 to 15, the Pentoxylierungsgrad usually 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2. The Gesamtalkoxylierungsgrad, d , H. the sum of EO and PeO units is generally 1.5 to 70, preferably 4.5 to 29 and in particular 6.5 to 17. However, if the EO blocks are arranged terminally, the ratio of PeO blocks is less critical to EO blocks and is usually 1: 50 to 1: 3, preferably 1: 25 to 1: 5. The degree of ethoxylation is generally 3 to 50, preferably 4 to 25 and in particular 5 to 15, the degree of pentoxylation usually 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2. The Gesamtalkoxylierungsgrad amounts to usually 3.5 to 70, preferably 4.5 to 45 and in particular 5.5 to 17.

From the above statements it follows that in particular the ci-oxo alcohols or cio-oxo alcohols to be used according to the invention are based on olefins which are already branched. In other words, branching is not due solely to the hydroformylation reaction, as would be the case with the hydroformylation of straight-chain olefins. Therefore, the degree of branching according to the invention to be used alkoxylates is usually greater than 1.

The alkoxylates to be used according to the invention generally have a relatively low contact angle. Particularly preferred are alkoxylates whose contact angle is less than 120 ° and preferably less than 100 ° when it is determined using a 2 wt .-% alkoxylate-containing aqueous solution on a paraffin surface in a conventional manner.

The surface-active properties of the polyalkoxylates depend on one aspect of the type and distribution of the polyalkoxylate grouping. The surface tension, which can be determined according to the pendant drop method, is to be used according to the invention. alkoxylate is preferably in a range from 25 to 70 in N / m and in particular 28 to 50 in N / m for a solution containing 0.1% by weight of polyalkoxylate, in a range from 25 to 70 mN / m and in particular 28 to 45 mN / m for a 0.5 wt.% Polyalkoxylat containing solution. Polyalkoxylates preferably to be used according to the invention therefore qualify as amphiphilic substances.

Typical commercial products of the formula (I) are familiar to the person skilled in the art. They are z. BASF from the company under the common brand name of "Lutensole" offered, which differs depending on the basic alcohol Lutensole series A, AO, AT, ON, AP and FA .. Further added numbers indicate the degree of ethoxylation. B. "Lutensol AO 8" a C13-15-oxo-alcohol with eight EO units. "Lutensol ED" stands for a range of alkoxylated amines.

Further examples of polyalkoxylates according to the invention are products of the company Akzo, z. . As the "Ethylan" series of linear or branched alcohols based Thus, for example, "Ethylan SN 120" CIO ₁₂ alcohol with ten EO units, and "Ethylan 4 S" is a C _2-. - ₁₄ alcohol with four EO units.

Further examples of polyalkoxylates according to the invention are also the "NP" products from Akzo (formerly Witco) based on nonylphenols.

Further examples of polyalkoxylates according to the invention are castor oil ethoxylates (ricin oil EOx), z. B. Products of the "Emulphon CO" or "Emulphon EL" product series from Akzo, such as "Emulphon CO 150" with 15 EO units, or products of the "Ethomee" series based on coconut oil amines or tallow fatty amines (US Pat. "Tallow oil amines"), eg "Ethomee C / 25", a coconut fatty amine with 25 EO units.

Alkoxylates according to the invention also include so-called "narrow range" products. The term "narrow ranks" here refers to a narrower distribution of the number of EO units. These include z. B. Products of the "Berol" series from Akzo.

Also suitable according to the invention are sorbitan ester ethoxylates, eg. B. "Armotan AL 69-66 POE (30) sorbitan monotallate", ie an esterified with sorbitol and then ethoxylated unsaturated fatty acid. It is also possible to use mixtures of different polyalkoxylates as component (a).

According to a particular embodiment of the invention, the formulation contains at least 20 wt .-%, preferably at least 25 wt .-% and in particular at least 30 wt .-% alkoxylate.

According to a further particular embodiment of the invention, the formulation contains at most 70% by weight, preferably at most 60% by weight and in particular at most 45% by weight. Alkoxylate.

As carrier component (b) it is generally possible to use solid, relatively high molecular weight, for example polymeric or macromolecular, organic sulfonates. The term sulfonate here stands for a salt which is composed of sulfonate anions and suitable cations.

It is particularly preferred in this case if the higher molecular weight sulfonate is water-soluble. Thus, in contrast to typical carriers which are generally based on water-insoluble inorganic solids, the sulfonates according to the invention can be introduced in dissolved form, preferably as aqueous concentrates, in the preparation of the solid formulations, whereby they are particularly effective as carriers of component (a). act.

Suitable relatively high molecular weight sulfonates generally have a weight-average molecular weight (determined by polystyrene sulfonates calibrated gel permeation chromatography) of at least about 1 kDa, preferably at least about 2.5 and in particular at least about 5 kDa, for example a weight-average molecular weight of about 6 - 7 kDa (eg "Tamol NN" series), or about 20 kDa (eg "Tamar NH" series). In another aspect, suitable higher molecular weight sulfonates have, for example, a number average molecular weight (as determined by polystyrene sulfonate calibrated gel permeation chromatography) of about 1 kDa (eg, "Tamol NN" series), or about 2 kDa (eg. B. "Tamol NH" series), so that the polydispersion index of suitable higher molecular weight sulfonates usually in a range of about 2 to 20 and preferably in a range of 5 to 15, for example at about 6 (z. Eg "Tamol NN" series), or about 20 (eg "Tamol NH" series). Further properties of suitable higher molecular weight sulfonates are, for example, Example, a bulk density of about 450 - about 550 g / 1 for solids or a density of about 1, 17 - about 1, 23 g / ml and a viscosity of about 20 - about 80 mPa ^■ s for Liquids and a neutral to alkaline behavior (pH in aqueous solution about 7 - 10).

According to a preferred embodiment of the invention lignosulfonates are used.

Lignosulfonates are prepared from lignin, which in turn is produced in plants, especially woody plants, by polymerization from three types of phenylpropanol monomers:

A) 3- (4-hydroxyphenyl) -2-propen-1-ol (p-coumaryl alcohol),

B) 3- (3-methoxy-4-hydroxyphenyl) -2-propen-1-ol (coniferyl alcohol), C) 3- (3,5-dimethoxy-4-hydroxyphenyl) -2-propen-1-ol (sinapyl alcohol ).

The first step in the construction of the macromolecular lignin structure is the enzymatic dehydrogenation of these monomers to form phenoxyl radicals. Random coupling reactions between these radicals result in a three-dimensional, amorphous polymer that, unlike most other biopolymers, does not have regularly ordered or repeating units. For this reason, no defined lignin structure can be named, although various models for an "average" structure have been proposed. Since the monomers of lignin contain nine carbon atoms, the analytical data are often expressed in terms of Cg formulas, eg CgH ₈₃ θ ₂ τ (OCH ₃ ) ₀ 9τ for lignin from Picea abies, and C ₉ H _{8 Z} O ₂ Q (OCH ₃ ) _{! 58} for lignin from Eucalyptus regnans.

The heterogeneity of lignin between plants of different taxa, as well as between the different tissues, cells and cell wall layers of each species, will be apparent to those skilled in the art. Lignins from softwoods, deciduous trees and grasses differ in terms of their content of guaiacyl (3-ιmeth- oxy-4-hydroxyphenyl), syringyl (3,5-dimethoxy-4-hydroxyphenyl) and 4-hydroxyphenyl -Units. Coniferous lignins consist mainly of coniferyl alcohol, while deciduous lignins consist of guaiacyl and syringyl units in various proportions, with deciduous trees having a much more variable lignin composition than softwoods. The methoxyl content more typical Hardwood lignin varies between 1.20 and 1.52 methoxyl groups per phenylpropane unit. Herbaceous plant lignins generally have a low content of syringylpropanes, with a ratio of methoxyl: Cg units below 1.

The composition of lignin also depends on age, e.g. in poplars, the ratio of syringyl to guaiacyl in mature xylem is higher than in younger xylem or phloem, and of the morphological location of lignin in cell wall. For example, in the birch, the lignin in the secondary cell wall of fiber cells consists mainly of syringyl units, while in the middle lamellae and cell angles of the fibers, it mainly comprises guaiacyl units. Lignin from wood under tension, in deciduous trees in the upper parts of branches and branches, contains more syringylpropane units than lignin from normal wood; wood under pressure, in coniferous trees in the lower parts of the branches and branches, however, is richer in 4-hydroxyphenyl units.

More than two thirds of the phenylpropane units in lignin are linked by ether bonds, the rest by carbon-carbon bonds.

The chemical behavior of lignin is determined mainly by the presence of phenolic, benzylic and carbonylic hydroxyl groups, the frequency of which may vary depending on the factors mentioned above and the isolation method.

Lignosulfonates are formed as by-products of pulp production under the

Influence of sulphurous acid, which causes sulphonation and a degree of demethylation of the lignins. Like the lignins, they are diverse in structure and composition. In water, they are soluble in the entire pH range, but insoluble in ethanol, acetone and other common organic solvents. Typical of softwood lignosulfonates is the following Cg formula:

C ₉ H ₈₅ O ₂₅ (OCH ₃₎ O ₈₅ (SO ₃ H) _04; e ₂₈₀ = 3.0 * 10 ³ L (C ₉ mass unit) ^"1 cm ^"1; λ _max = 280 nm; Phenolic hydroxyl content 0.5 meq./g.

Lignosulfonates are only slightly surface-active. They have little tendency to reduce the interfacial tension between liquids and are not suitable for reducing the surface tension of the water or for micelle formation. As dispersing agents, they can function by adsorption / desorption and charge formation of substrates. However, their surface activity can be increased by incorporation of long-chain alkylamines into the lignin structure.

Methods for the isolation and purification of lignosulfonates are familiar to the person skilled in the art. The Howard process precipitates calcium lignosulfonates by adding excess lime to spent sulfite leaching. Lignin sulfonates can also be isolated by forming insoluble quaternary ammonium salts with long-chain amines. On an industrial scale, ultrafiltration and ion exchange chromatography can be used to purify lignosulfonates.

Lignosulfonate series useful in the present invention are commercially available under various trade names, e.g. Ameri-Bond, Dynasperse, KeNg, Lignosol, Marasperse, Norlig (Daishowa Chemicals), Lignosite (Georgia Pacific), Reax (MEAD Westvaco), Wafolin, Wafex, Wargotan, Wanin, Wargonin (Holmens), Vanillex (Nippon Paper), Vanisperse , Vanicell, Ultrazine, Ufoxane (Borregaard), Serla-Bondex, Serla-Con, Serla-Pon, Serla-Sol (Serlachius), Collex, Zewa (Wadhof-Holmes), Raylig (ITT Rayonier).

According to a further preferred embodiment of the invention, synthetic polymeric sulfonates are used as component (b).

It is again particularly preferred in this case if the higher molecular weight sulfonate is a condensation product based on a sulfonated aromatic, an aldehyde and / or ketone, and optionally a compound selected from undulfonated aromatics, urea and urea derivatives.

In this case, it is particularly preferred if the sulfonated aromatic is selected from naphthalenesulfonic acids, indansulfonic acids, tetralinsulfonic acids, phenolsulfonic acids, di- and polyhydroxybenzenesulfonic acids, sulfonated ditolyl ethers, sulfomethylated 4,4'-dihydroxydiphenylsulfones, sulfonated diphenylmethane, sulfonated biphenyl, sulfonated hydroxybiphenyl, sulfonated terpenyl and benzenesulfonic acids. It is also particularly preferred if the aldehyde and / or the ketone is / are selected from aliphatic dC ₅ -aldehydes or C ₃ -C ₅ -ketones. Again, it is particularly preferred if the aliphatic CrC ₅ aldehyde is formaldehyde.

It is furthermore particularly preferred if the non-sulfonated aromatic is chosen from phenol, cresol and dihydroxydiphenylmethane. It is further particularly preferred if the urea derivative is selected from dimethylolurea, melamine and guanidine.

In a particular embodiment, the condensation product comprises repeat units of the formula (IIa):

and / or formula (IIb):

and / or formula (Mc)

wherein

R ^{8 is} hydrogen, one or more hydroxyl groups or one or more Ci-β-alkyl radicals;

q1 corresponds to a value of 100 to 10; and A is methylene, 1, 1-ethylene or a group of the formulas

-CH ₂ -NH-CO-NH-CH ₂ -, -CH-NH-CO-NH-CH-

CH '3, C ^ H ¹ 3, stands. In the above formulas, the positions of the bonds are not fixed.

Preferably, A is methylene. It is likewise preferred if R ^{8 is} hydrogen or up to 3 C 1-β-alkyl radicals, for example 1 or 2-C ₄ -alkyl radicals.

Such condensation products and the processes and apparatus for their preparation are familiar to the person skilled in the art.

In a further particular embodiment, the condensation product comprises repeat units of the formula (III):

wherein

R ^{9 is} hydrogen, one or more hydroxyl groups or one or more Ci_8-alkyl radicals;

q2 corresponds to a value of 100 to 10 1 ^ι 0 ^υ ;

for methylene, 1, 1-ethylene or a group of the formulas

-CH ₂ -NH-CO-NH-CH ₂ -, -CH-NH-CO-NH-CH-

It is preferred if R ^{9 is} a hydroxyl group. In a further particular embodiment, the sulfonate is selected from condensation products of phenolsulfonic acid, formaldehyde and urea. Preferably, such condensation products comprise repeat units of the formula (IIIa):

wherein

q2 corresponds to a value of 100 to 10 ¹⁰ .

Such condensation products and the processes and apparatus for their preparation are also known to the person skilled in the art.

A further embodiment of relatively high molecular weight sulfonates is provided by copolymers CP composed of ethylenically unsaturated monomers M, the monomers M α) constituting the copolymer CP comprising at least one monoethylenically unsaturated monomer M1 having at least one sulfonic acid group, and β) at least one neutral, monoethylenically unsaturated monomer M2.

The copolymers CP are usually so-called random copolymers, i. the monomers M1 and M2 are randomly distributed along the polymer chain. In principle, alternating copolymers CP and block copolymers CP are also suitable.

According to the invention, the monomers M constituting the copolymer CP comprise at least one monoethylenically unsaturated monomer M1 which has at least one sulfonic acid group. The proportion of the monomers M1 to the monomers M generally makes 1 to 90% by weight, frequently 1 to 80% by weight, in particular 2 to 70 Wt .-% and especially 5 to 60 wt .-%, based on the total amount of monomers M out.

Suitable monomers M1 are in principle all monoethylenically unsaturated monomers which have at least one sulfonic acid group. The monomers M1 can be present both in their acid form and in the salt form. The specified parts by weight refer to the acid form.

Examples of monomers M1 are styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid and the monomers defined by the following general formula (V) and the salts of the abovementioned monomers.

In formula (V): n is 0, 1, 2 or 3, in particular 1 or 2; X is O or NR ^15;

R ^{12 is} hydrogen or methyl;

R ¹³ , R ¹⁴ independently of one another are hydrogen or C 1 -C ₄ -alkyl, in particular hydrogen or methyl and

RR ¹¹⁵⁵ hydrogen or C 1 -C ₄ -alkyl, in particular hydrogen.

Examples of monomers M1 of the general formula (V) are 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidoethanesulfonic acid, 2-methacrylamidoethanesulfonic acid, 2-acryloxethanesulfonic acid, 2-methacryloxethanesulfonic acid, 3-acryloxypropanesulfonic acid and 2-methacryloxypropanesulfonic acid.

In addition to the monomers M1, the monomers C constituting the copolymer CP comprise at least one neutral monoethylenically unsaturated monomer M2. Neutral means that the monomers M2 have no functional group which is acidic or basic in the aqueous phase or in ionic form. The total amount of Monomer M2 usually accounts for 10 to 99 wt .-%, often 20 to 99 wt .-%, in particular 30 to 98 wt .-% and especially 40 to 95 wt .-%, based on the total weight of the monomers M from.

Examples of monomers M2 are those with limited water solubility, e.g. a water solubility below 50 g / l and in particular below 30 g / l (at 20 ° C and 1013 mbar) and those with an increased water solubility, e.g. a water solubility ≥ 50 g / l, in particular ≥ 80 g / l (at 20 ° C and 1013 mbar). Monomers with limited water solubility are also referred to below as monomers M2a. Monomers with increased water solubility are also referred to below as monomers M2b.

Examples of monomers M2a are vinylaromatic monomers such as styrene and styrene derivatives such as α-methylstyrene, vinyltoluene, ortho-, meta- and para-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene and the corresponding halogenated vinylaromatic monomers, α-olefins with 2 to 12 carbon atoms such as ethene, propene, 1-butene, 1-pentene, 1-hexene, isobutene, diisobutene and the like, dienes such as butadiene and isoprene, vinyl esters of aliphatic Ci-Ci ₈ carboxylic acids such as vinyl acetate, vinyl propionate, vinyl laurate and Vinyl stearate, vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, mono- and di-C 1 -C ₂₄ -alkyl esters of monoethylenically unsaturated monocarboxylic and dicarboxylic acids, for example of acrylic acid, methacrylic acid, fumaric acid, maleic acid or itaconic acid, mono- and di-C ₅ -C ₂ cycloalkyl esters of the aforementioned monoethylenically unsaturated mono- and dicarboxylic acids, mono- and diesters of the aforementioned monoethylenically unsaturated Alkanols mono- and dicarboxylic acids, phenyl-CrC ₄ or phenoxy -C ₄ -alkanols, further monoethylenically unsaturated ethers, in particular ₂ dC o-alkyl vinyl ethers such as ethyl vinyl ether, methyl vinyl ether, n-butyl vinyl ether, octadecyl vinyl ether, Triethylenglykolvinylmethylether, vinyl isobutyl ether, Vinyl (2-ethylhexyl) ethers, vinyl propyl ethers, vinyl isopropyl ethers, vinyldodecyl ethers, vinyl tert-butyl ethers.

The monomers M2a are preferably selected from vinylaromatic monomers, esters of acrylic acid with C ₂ -C 10 -alkanols, such as ethyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, esters of acrylic acid with C C ₄ -C 10 -cycloalkanols such as cyclohexyl acrylate, esters of acrylic acid with phenyl-C ₁ -C ₄ -alkanols such as benzyl acrylate, 2-phenylethyl acrylate and 1-phenylethyl acrylate, esters of acrylic acid with phenoxy-C 1 -C ₄ -alkanols such as 2-phenoxyethyl acrylate, the esters of Methacrylic acid with C 1 -C 10 -alkanols, in particular with C 1 -C ₆ -alkanols, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, esters of methacrylic acid with C ₄ - alkanols Ci ₀ cycloalkanols such as cyclohexyl methacrylate, esters of methacrylic acid with Phe nyl-CrC ₄ such as benzyl, 2-phenylethyl and 1-phenylethyl methacrylate, and esters of methacrylic acid with alkanols of phenoxy-CrC ₄ as 2- phenoxyethyl. In a particularly preferred embodiment, the monomers M2a comprise at least 80%, based on the total amount of the monomers M2a and in particular exclusively esters of acrylic acid and / or methacrylic acid with dC ₆ alkanols.

Neutral monoethylenically unsaturated monomers having increased water solubility or even water miscibility are known to the person skilled in the art, for example from Ullmann's Encyclopedia of Industrial Chemistry, "Polyacrylates", 5th ed. On CD-ROM, Wiley-VCH, Weinheim 1997. Typical monomers M2b are hydroxylated C ₂ -C ₄ -alkyl esters of monoethylenically unsaturated monocarboxylic acids, in particular of acrylic acid and of methacrylic acid, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, furthermore amides of monoethylenically unsaturated monocarboxylic acids such as acrylamide, methacrylamide, furthermore acrylonitrile and methacrylonitrile, N-vinyllactams such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylamides aliphatic CrC ₄ - Monocarboxylic acids such as N-vinylformamide, N-vinylacetamide, monoethylenically unsaturated, Urea group-carrying monomers such as N-vinyl- and N-allylurea and derivatives of imidazolidin-2-one, for example N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethylimidazolidin-2-one, N-allyloxyethyl-imidazolidine-2 -on N- (2-acrylamidoethyl) imidazolidin-2-one, N- (2-acryloxyethyl) imidazolidin-2-one, N- (2-methacrylamidoethyl) imidazolidin-2-one, N- (2-methacryloxyethyl) imidazolidine 2-one (= ureidomethacrylate), N- [2- (acryloxyacetamido) ethyl] imidazolidin-2-one, N- [2- (2-acryloxyacetamido) ethyl] imidazolidin-2-one N- [2- (2-meth acryloxyacetamido) ethyl] imidazolidin-2-one; and the same. Preferably, the monomers are selected from hydroxy-M2b -C ₄ alkyl esters of acrylic acid and of methacrylic acid, acrylamide, methacrylamide, acrylonitrile, N-vinyl lactams, said hydroxy-C ₂ -C ₄ alkyl esters of acrylic acid and methacrylic acid particularly preferred. In particular, the monomers M2b comprise at least 80% by weight, based on the total amount of the monomers M2b, of at least one hydroxy-C ₂ -C ₄ -alkyl ester of acrylic acid and / or methacrylic acid.

Preferably, the monomers M2 comprise at least one of the aforementioned monomers M2a, which has a solubility below 50 g / l and especially below 30 g / l at 20 ° C in water. The proportion of monomers M2a to the copolymer CP constituent monomers M is typically in the range of 10 to 99 wt .-%, often in the range of 20 to 99 wt .-%, in particular in the range of 30 to 98 wt .-% and especially in the range from 40 to 95% by weight, based on the total weight of monomers M.

In a first preferred embodiment of the invention, the monomer M2a is sole or nearly sole monomer M2 and constitutes at least 95% by weight and in particular at least 99% by weight of the monomers M2.

In a second preferred embodiment of the invention, the monomers M2 comprise, in addition to the monomer M2a, at least one monomer M2b which has a solubility of at least 50 g / l and especially at least 80 g / l at 20 ° C in water. Correspondingly, the monomers M constituting the copolymer CP comprise, in addition to the monomer M1, at least one of the aforementioned monomers M2a, in particular at least one of the monomers M2a mentioned as preferred and at least one of the aforementioned monomers M2b, in particular at least one of the monomers M2b mentioned as preferred.

Frequently, the total amount of monomers M1 + M2b will not exceed 90% by weight, in particular 80% by weight and especially 70% by weight, based on the total amount of monomers M, and is in particular in the range from 10 to 90% by weight. %, in particular in the range from 20 to 80% by weight and especially in the range from 30 to 70% by weight, based on the total amount of the monomers M. Accordingly, the monomers M2a often make up at least 10% by weight, in particular at least 20 wt .-% and especially at least 30 wt .-%, for example 10 to 90 wt .-%, in particular 20 to 80 wt .-%, and especially 30 to 70 wt .-%, based on the total amount of the monomers M, from.

In this second, particularly preferred embodiment, the monomers M1 preferably make 1 to 80% by weight, in particular 2 to 70% by weight and particularly preferably 5 to 60% by weight, the monomers M2a preferably 10 to 90% by weight. , in particular der from 20 to 80 wt .-% and particularly preferably 30 to 70 wt .-%, and the monomers M2b preferably 5 to 89 wt .-%, in particular 10 to 78 wt .-% and particularly preferably 20 to 65 wt .-% , based on the total amount of monomers M from. Particularly preferred among these copolymers are CP whose constituent monomers M as monomers M1 at least one monomer of formula (V), as monomers M2a at least one selected from esters of acrylic acid with C ₂ -C ₀ alkanols and esters of methacrylic acid with d-Cio Alkanols selected monomer and as monomers M2b at least one selected from hydroxy-C ₂ -C ₄ alkyl esters of acrylic acid and methacrylic acid selected monomer.

In addition, the monomers M which constitute the copolymer may also comprise further monomers M3 other than the monomers M1 and M2. The proportion of the monomers M3 in the total amount of the monomers M is preferably not more than 40 wt .-%, in particular not more than 20 wt .-% of. In a preferred embodiment, the monomers comprise no or not more than 3% by weight, especially not more than 1% by weight of monomers M3 other than monomers M1 and M2.

The monomers M3 include monoethylenically unsaturated monomers having at least one carboxylic acid group, in particular monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 6 C atoms (monomers M3a) such as acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid and the like, and the anhydrides of the abovementioned monoethylenically unsaturated dicarboxylic acids, the proportion of the monomers M3a generally not exceeding 20% by weight and in particular 10% by weight, based on the total monomer amount M.

The monomers M3 furthermore include polyethylenically unsaturated monomers (M3b). The proportion of such monomers M3 will generally be not more than 2% by weight and in particular not more than 0.5% by weight, based on the total amount of monomers M. Examples of these are vinyl and allyl esters of monoethylenically unsaturated carboxylic acids such as allyl acrylate and allyl methacrylate, di- and polyacrylates of diol polyols such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diglycol, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol trimethacrylate, tris (hydroxymethyl) ethane triacrylate and trimethacrylate, pentaerythritol triacrylate and trimethacrylate, and allyl and methallyl esters of polyfunctional carboxylic acids, such as diallyl maleate, diallyl fumarate, diallyl phthalate. Typical monomers M3b are also compounds such as divinylbenzene, di-vinylurea, diallylurea, triallyl cyanurate, N, N'-divinyl and N, N'-diallylimidazolidin-2-one, as well as methylenebisacrylamide and methylenebismethacrylamide.

According to the invention, copolymers CP which have a number average molecular weight M _n in the range from 1000 to 500,000 daltons, in particular 2,000 to 50,000 daltons and especially 5,000 to 20,000 daltons are also preferred. The weight-average molecular weight is often in the range of 2,000 to 1,000,000 daltons, in particular 4,000 to 100,000 daltons and especially 10,000 to 50,000 daltons. The ratio MJM _n is often in the range of 1, 1: 1 to 10: 1, in particular in the range of 1, 2: 1 to 5: 1. The molecular weights M _w and M _n and the nonuniformity of the polymers are determined by size exclusion chromatography (= gel permeation chromatography or GPC for short). Commercially available polymethylmethacrylate (PMMA) calibration kits can be used as the calibration material.

In general, the copolymer of the invention will have a glass transition temperature T _g in the range of -80 to 160 ° C and often in the range of -40 ° C to + 100 ° C. The glass transition temperature T _g is understood here to be the midpoint temperature determined by differential thermal analysis (DSC) in accordance with ASTM D 3418-82 (compare Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A 21, VCH Weinheim 1992, page 169 and Zosel , Paint and varnish 82 (1976), pp. 125-134, see also DIN 53765).

In this context, it has been found to be useful to measure the glass transition temperature T _{g of} the copolymer CP using the equation of Fox (TG Fox, Bull. Am. Phys.

Soc. (Ser. II) 1, 123 [1956] and Ullmann's Encyclopedia of Industrial Chemistry, Weinheim (1980), pp 17-18) on the basis of the glass transition temperature of the respective homopolymers of the monomers M constituting the polymer. The latter are z. From Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) p. 169 or J. Brandrup, E.H. Immergut, Polymer Handbook 3rd ed., J. Wiley, New York 1989.

The copolymers CP according to the invention are known in part from PCT / EP 04/01 1797 or can be prepared by conventional methods by radical polymerization of the monomers M. The polymerization can be carried out by free radical polymerization or by controlled radical polymerization. The polymerization is carried out using one or more initiators and can be carried out as a solution polymerization, as an emulsion polymerization, as a suspension polymerization or as a precipitation polymerization or in bulk. The polymerization can be carried out as a batch reaction, in a semicontinuous or continuous procedure.

The reaction times are generally in the range between 1 and 12 hours. The temperature range in which the reactions can be carried out is generally from 20 to 200 ° C, preferably from 40 to 120 ° C. The polymerization pressure is of minor importance and may be in the range of normal pressure or slight negative pressure, e.g. > 800 mbar or at overpressure, e.g. to 10 bar, with higher or lower pressures can also be applied.

As initiators for the free-radical polymerization customary radical-forming substances are used. Preference is given to initiators from the group of the azo compounds, the peroxide compounds or the hydroperoxide compounds. Examples which may be mentioned are acetyl peroxide, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxy-isobutyrate, caproyl peroxide, cumene hydroperoxide, 2,2'-azobis-isobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2 -methyl-N - (- 2-hydroxyethyl) propionamide, 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, Particular preference is given to azobisisobutyronitrile (AIBN). The initiator is customarily employed in an amount of 0.02 to 5% by weight and in particular 0.05 to 3% by weight, based on the amount of .alpha Monomers M. The optimum amount of initiator naturally depends on the initiator system used and can be determined by the person skilled in the art in routine experiments.The initiator can be initially or partially charged in the reaction vessel B. 80 to 100% of the initiator in the course of the polymerization in the polymerization sreaktor.

Of course, the molecular weight of the copolymers CP by adding regulators in a small amount, for. B. 0.01 to 5 wt .-%, based on the polymerizing monomers M, can be adjusted. Suitable regulators are, in particular, organic thio compounds, for example mercaptoalcohols, such as mercaptoethanol, mercaptocarboxylic acids, such as thioglycolic acid, mercaptopropionic acid, alkyl mercaptans, such as dodecylmercaptan, furthermore allyl alcohols and aldehydes. In particular, the preparation of the copolymers CP is carried out by free-radical solution polymerization in a solvent. Examples of solvents are water, alcohols, such as. Methanol, ethanol, n-propanol and isopropanol, dipolar aprotic solvents, e.g. B. N-alkyl lactams such as N-methylpyrrolidone (NMP), N-ethylpyrrolidone, furthermore dimethyl sulfoxide (DMSO), N, N-dialkylamides of aliphatic carboxylic acids such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, furthermore aromatic, aliphati - and cycloaliphatic hydrocarbons which may be halogenated, such as hexane, chlorobenzene, toluene or benzene. Preferred solvents are isopropanol, methanol, toluene, DMF, NMP, DMSO and hexane, particularly preferred is DMF.

As salts, the sulfonates contain cations in stoichiometric amount. Examples of suitable cations are alkali metal cations such as Na ⁺ or K ⁺ , alkaline earth metal ions such as Ca ²⁺ and Mg ²⁺ , furthermore ammonium ions such as NH ₄ ⁺ , tetraalkylammonium cations such as tetramethylammonium, tetraethylammonium and tetrabutylammonium, furthermore protonated primary, secondary and tertiary amines, especially such that 1, 2 or 3 radicals selected from -C ₂ -alkyl groups and hydroxyethyl carry, for example, the protonated forms of mono-, di- and tributylamine, propylamine, min Diisopropyla-, hexylamine, dodecylamine, oleylamine, stearylamine, ethoxylated oleylamine , ethoxi- profiled stearylamine, ethanolamine, diethanolamine, triethanolamine or N ₁ N-dimethylethanolamine.

In a preferred embodiment of the invention, the sulfonate is an ammonium, alkali metal, alkaline earth metal or transition metal sulfonate.

It is particularly preferred in each case when the alkali metal is sodium or potassium, the alkaline earth metal is calcium or magnesium and the transition metal is copper.

It is also possible to use mixtures of different sulfonates as component (b).

Suitable sulfonates are familiar to the expert and z. B. under the name "Tamol" and "Setamol" from BASF.

Examples of sulfonic acid-containing polymers which are in principle suitable as component (b) are also mentioned in EP 707445. It is particularly preferred in this case if the formulation contains at least 15 wt .-%, preferably at least 25 wt .-% and in particular at least 30 wt .-% higher molecular weight sulfonate.

It is particularly preferred in this case if the formulation is not more than 80

Wt .-%, preferably at most 70 wt .-% and in particular at most 55 wt .-% higher molecular weight sulfonate.

The solid formulations according to the invention contain relatively high amounts of polyalkoxylate. Based on the amount of higher molecular weight sulfonate, it is preferred that the weight ratio of liquid or low melting polyalkoxylate to higher molecular weight sulfonate is at least 3:10, preferably at least 1: 3 and most preferably 1: 2. However, the ratio of liquid or low melting polyalkoxylate to higher molecular weight sulfonate should not be more than 3: 1, preferably not more than 2: 1.

In one embodiment of the invention, part of the sulfonate in the carrier component (b) may be replaced by inorganic solid. In this embodiment, component (b) in addition to the higher molecular weight sulfonate (b1) nor inorganic solid (b2).

Suitable inorganic solids in the carrier component (b) are, in particular, those which are usually used in solid formulations for receiving liquid or low-melting auxiliaries, in particular oily auxiliaries, such as the polyalkoxylates according to the invention ("carriers") Suitable inorganic solids are generally sparingly soluble in water or insoluble in water, ie for dissolving a portion of inorganic solid at 20 ° C at least 100, usually at least 1000 and in particular At least 10,000 parts of water are required, but the sparingly soluble or even water-insoluble inorganic solids may be water-swellable.

The inorganic solids include, in particular, aluminum oxide-based substances, in particular aluminum oxide and bauxite, silicon dioxide-based substances, in particular silicates and silicate minerals, especially diatomaceous earths (kieselguhr, diatomite), silicic acids, pyrophyllite, talc, mica and clays such as kaolinite, bentonite, montmoronic acid. morillonite and attapulgite. In principle, there are also some inorganic salts such as alkaline earth metal carbonates, in particular calcium carbonates (lime, chalk) and magnesium carbonates and calcium magnesium carbonates, and alkaline earth metal sulfates, especially calcium sulfates (eg gypsum). Among the silicates are, for example, the products of the Sipernat series (Degussa), in particular Sipernat 22S or 5OS, which can typically be used for this purpose.

However, according to the invention, the proportion of the inorganic solids listed above as component (b2) can be chosen to be comparatively low, since essentially the higher molecular weight sulfonates function as carriers of the polyalkoxylates. In addition, avoiding high levels of inorganic solids, there are further advantages.

In this sense, the weight-based proportion of the higher molecular weight sulfonate to the component (b) is usually greater than the weight-based proportion of inorganic solid; According to the invention, the weight ratio of higher molecular weight sulfonate to inorganic solid is preferably at least 2, preferably at least 5 and in particular at least 10.

In particular, it is preferred that the formulation contains less than 10% by weight in total, in particular less than 5% by weight of aluminum-based substances, and particularly preferred if the formulation as a whole is substantially free of aluminum-based substances.

It is also preferred if the formulation contains less than 5% by weight in total, more preferably less than 2% by weight of diatomaceous earth, and most preferably, if the formulation as a whole is substantially free of diatomaceous earth. It is also preferred if the formulation as a whole contains less than 5% by weight, in particular less than 1% by weight of kaolinite, and particularly preferred if the formulation as a whole is substantially free of kaolinite. It is also preferred that the formulation contains less than 5% by weight in total, more preferably less than 1% by weight of bentonites, and particularly preferred when the formulation as a whole is substantially free of bentonites. It is also preferred that the formulation contains less than 7.5% by weight in total, more preferably less than 1.5% by weight of clays, and particularly preferred when the formulation is substantially free of clays.

It is also preferred that the formulation contains less than 15% by weight in total, in particular less than 2% by weight, of silicon dioxide-based substances, and particularly preferred if the formulation is substantially free of silicon dioxide-based substances.

According to a particular embodiment, the formulation contains a total of less than 15 wt .-%, in particular less than 10 wt .-% and particularly preferably less than 5 wt.% Of the following inorganic solids: alumina-based substances, in particular alumina and bauxite, silicon dioxide-based substances, in particular Silicates and silicate minerals, in particular diatomaceous earths (kieselguhr, diatomite), silicic acids, pyrophyllite, talc, mica and clays such as kaolinite, ben- tonite, montmorillonite and attapulgite.

It is preferred if the formulation as a whole contains less than 1% by weight of sorbents, and particularly preferred if the formulation as a whole is substantially free of sorbents.

It is furthermore preferred if the formulation contains less than 5% by weight, in particular less than 1% by weight, of calcium carbonate, and particularly preferably if the formulation as a whole is substantially free of calcium carbonate. Further, it is also preferred that the formulation contains less than 5% by weight in total, in particular less than 1% by weight of magnesium carbonate, and particularly preferred when the formulation as a whole is substantially free of magnesium carbonate.

According to a particular embodiment, the formulation as a whole contains less than 10% by weight, in particular less than 5% by weight and particularly preferably less than 1% by weight of the following inorganic solids: alkali metal and alkaline earth metal carbonates, in particular calcium carbonates (lime, Chalk) and magnesium carbonates and calcium magnesium carbonates, and alkali and alkaline earth metal sulfates, in particular calcium sulfates (eg gypsum). It is very particularly preferred in this case if the formulation is not more than 15 wt .-%, preferably at most 10 wt .-% and especially at most 5 wt .-%, z. B. contains at most 1 wt .-% inorganic solid, and in particular when the carrier component (b) is substantially free of inorganic solid.

According to a particular embodiment, the present invention relates to a solid formulation which, in addition to the components a) and b), may comprise further adjuvant as component c).

The optional component (c) can serve many purposes. In general, therefore, component (c) consists of a combination of several substances with different functions and properties. The choice of suitable auxiliaries is carried out according to the requirements usually by a person skilled in the art.

As component (c) are in particular:

(d) surfactants;

(c2) antisettling agents, antifoam agents, retention aids, pH buffers, antidrip agents and other auxiliaries to improve the handling and / or physical properties of the formulation; and (c3) chelating agent.

As used herein, the term "surfactant" (d) refers to surfactants such as surfactants, dispersants, emulsifiers or wetting agents.

In principle, anionic, cationic, amphoteric and nonionic surfactants are useful.

Examples of anionic surfactants include

Carboxylates, in particular alkali, alkaline earth and ammonium salts of fatty acids; Acylglutamates;

Sarcosinates, eg sodium lauroyl sarcosinate; taurates;

Methylcelluloses;

Alkyl phosphates, e.g. For example, mono- and diphosphoric acid alkyl esters; Sulfate; - Monomeric sulfonates, especially alkyl and alkylarylsulfonates, especially

Alkali metal, alkaline earth metal and ammonium salts of arylsulfonic acids and alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids, such as, for example, phenolsulfonic acids, naphthalene and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, alkylnaphthalenesulfonates, alkylmethyl ester sulfonates, mono- or dialkylsuccinic acid sulfonates;

Protein hydrolysates and depleted lignin-sulphite waste liquors.

The cationic surfactants include, for example

- Quaternary ammonium salts, in particular alkyltrimethylammonium and di- alkyldimethylammonium halides and alkyl sulfates and pyridine and imidazoline derivatives, in particular alkylpyridinium halides.

The nonionic surfactants include in particular

Glycerol esters, such as glycerol monostearate; Sugar surfactants, in particular sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), and esters of monofunctional or polyfunctional alcohols, such as alkyl (poly) glycosides and N-alkylgluconamides; - Alkylmethylsulfoxide;

Alkyldimethylphosphine oxides such as, for example, tetradecyldimethylphosphinoxide;

Di-, tri- and multiblock polymers of the type (AB) x, ABA and BAB, e.g. polystyrene

Block polyethylene oxide, and AB comb polymers, e.g. Polymethacrylate comb-polyethylene oxide and in particular ethylene oxide-propylene oxide Blockcopoly- mers or their end-capped derivatives.

Examples of amphoteric surfactants include

- sulfobetaines;

Carboxy betaines and - Alkyldimethylaminoxide, eg Tetradecyldimethylaminoxid.

Other surfactants which may be mentioned here by way of example without being able to be assigned unambiguously to one of the groups mentioned include

Perfluorosurfactants, silicone surfactants,

Phospholipids, such as. As lecithin or chemically modified lecithins, amino acid surfactants, eg. N-lauryl glutamate, and - surface active homo- and copolymers, e.g. Polyvinylpyrrolidone, polyacrylic acids in the form of their salts, polyvinyl alcohol, polypropylene oxide, polyethylene oxide, maleic anhydride-isobutene copolymers and vinylpyrrolidone-vinyl acetate copolymers.

Other suitable wetting agents include: dioctylsulfosuccinate (eg "Pelex OTP"), dialkylsulfonimide ("Leophen RBD"), diisobutylnaphthalenesulfonate ("Nekal BX"), various alkylalkynols ("Surfynol", Bisterfeld), alkylarylphenol ethers - Phosphate ester ("Phospholan PNP") and polyethylene glycol ("Pluriol") and combinations of these substances.

The proportion of the surface-active auxiliary component (d) in the total weight of the formulation, if present, is generally up to 25% by weight, preferably up to 20% by weight, especially up to 15% by weight, and especially up to 10 wt .-%, based on the total mass of the formulation.

Such surface-active auxiliary components are z. T. contained in drug suspensions and preconcentrates, which are used in combination with the ingredients of the invention. Alternatively, they may be added separately in a suitable step of preparing the formulation.

The antifoams include, in particular, those of the silicone type, for example, sold by the company Wacker Silicon SL and the like.

The anti-settling agents, retention aids, pH buffers and antidriping agents comprise a variety of possible substances. They are familiar to the expert. Further aids from (c2) are z. As antidusting agents, supporting substances, polymers for improving the structure of granules, powdering agents or polymeric flow improvers for granules Such agents are described in the prior art and are familiar to the person skilled in the art Hydrophilic pyrogenic silicas such as the Aerosil brands (US Pat. Degussa) can also act as auxiliaries and / or flow improvers ("antiblocking agents").

The proportion of the surface-active auxiliary component (c2) in the total weight of the formulation, if present, is generally up to 15% by weight, preferably up to 10% by weight and in particular up to 5% by weight, based on the total mass of the formulation.

Preferred chelating agents are heavy metal and especially transition metal complexing compounds, e.g. EDTA and its derivatives.

If present, the proportion of component (c3) in the total weight of the formulation is generally from 0.001 to 0.5% by weight, preferably from 0.005 to 0.2% by weight and in particular from 0.01 to 0.1% by weight. %.

It is generally preferred if the formulation as a whole at most 60 wt .-%, preferably at most 45 wt .-% and in particular at most 30 wt .-%. contains further excipient (c).

Typically, the weight ratio of (a) and (b) to (c) is at least 3, preferably at least 5.

According to a particular embodiment, the present invention relates to a solid formulation which, in addition to the components a), b) and optionally c) as component d) may comprise water-soluble inorganic salt.

An inorganic salt is water-soluble if less than 20 parts of water, in particular less than 10 parts of water, are required to dissolve a part of inorganic salt at 20 ° C. Suitable water-soluble inorganic salt of component (d) are, in particular, those which are suitable for agricultural use, for example minerals and trace elements which can be used in plants. Suitable water-soluble inorganic salts are found especially among alkali metal and ammonium salts, particularly preferably sodium, potassium and ammonium sulfates, chlorides, carbonates, nitrates and phosphates, more preferably ammonium sulfate and ammonium hydrogen sulfate, and mixtures thereof. In a particular embodiment, component (d) consists essentially of ammonium sulfate.

If present, the proportion of component (d) in the total weight of the formulation may be up to 65% by weight. Their proportion of the total formulation is preferably up to 50% by weight, preferably up to 28.5% by weight and particularly preferably up to 25% by weight, for example 2% by weight. B. 0 wt .-% - 17.5 wt .-%.

Component (d) is particularly suitable as a solid basis for fluidized bed and fluidized bed granules. Accordingly, the water-soluble inorganic salt can serve as a core for the shaping process during the fluidized bed drying, since in the fluidized bed drying no de noi / o formation of defined particles from the fluid phase is possible without presenting a solid core attachment, or a fluidized bed process without the addition of solid cores does not lead to useful particle size distributions.

However, solid formulations with relatively small amounts of component d) represent a preferred embodiment. In this sense, the proportion of component d) in the overall formulation is up to 0 to 10 wt .-%, preferably 0 to 5 wt .-% and in particular 0 up to 2% by weight, e.g. B. 0 wt .-% - 1 wt .-%. In this embodiment, the still present water-soluble inorganic salts in the sense of the task of particular importance is usually not. Typically, they are included for manufacturing purposes, i. they are introduced together with other components of the invention.

Thus, it is preferred that the formulation contains less than 5% by weight in total, more preferably less than 2% by weight of sodium chloride, and particularly preferred when the formulation as a whole is substantially free of sodium chloride. Thus, it is also preferred that the formulation contains less than 5% by weight in total, more preferably less than 2% by weight of potassium chloride, and particularly preferred when the formulation as a whole is substantially free of potassium chloride. Thus, it is also preferable if the formulation as a whole contains less than 5% by weight, in particular especially less than 2% by weight of sodium carbonate, and most preferred when the formulation as a whole is substantially free of sodium carbonate. Thus, it is also preferred if the formulation contains less than 5% by weight in total, in particular less than 2% by weight of potassium hydrogenphosphate, and particularly preferred if the formulation as a whole is substantially free of potassium hydrogenphosphate.

According to a particular embodiment, the formulation contains a total of less than 10% by weight, in particular less than 5% by weight and particularly preferably less than 1% by weight of the following water-soluble inorganic solids: alkali metal and alkaline earth metal halides, in particular sodium chloride and potassium chloride , Alkali metal sulfates, e.g. For example, sodium sulfate, alkali metal carbonates, z. For example, sodium carbonate, and alkali and alkaline earth metal phosphates, especially potassium hydrogen phosphate.

In a particular embodiment of the invention, the formulation is substantially anhydrous, in particular having a water content of less than 5% and especially less than 2% of the total weight.

In a particular embodiment of the invention, the formulation is less hygroscopic, it being preferred if its moisture absorption at 65% humidity less than 20 wt .-%, preferably less than 15 wt .-%, and in particular less than 10 wt .-% is.

In a particular embodiment of the invention, the formulation is a particulate solid, in particular a granulate or a powder.

It is particularly preferred in this case if the granules are coarse-grained.

In this case, it is furthermore particularly preferred if the granules are selected from water-dispersible granules (WG) and water-soluble granules (SG), which may in particular be fluidized-bed granules (WSG).

Furthermore, it is particularly preferred if the powder is a dry-flowable (DF) powder, in particular a pourable or free-flowing powder, more preferably a powder having a particle size in the range from 1 to 200 microns, preferably in the range of 2 to 150 microns and in particular in the range of 5 to 100 microns, determined by the method CIPAC MT 59 ("dry sieve test").

In a particular embodiment of the invention, the formulation is essentially dust-free, determined by method CIPAC MT 171 ("dustiness of granular formulations").

In a particular embodiment of the invention, the formulation is essentially storage-stable, in particular does not stick to it during storage, in particular does not adhere to it for at least eight weeks 'storage, preferably at least twelve weeks' storage at a temperature in the range from -10 ° C. to 40 ° C. Method CIPAC MT 172 ("flowability of water").

In a particular embodiment of the invention, the formulation is dispersible in water, determined by the method CIPAC MT 174 ("dispersibility of water-dispersible granules").

Another object of the present invention is a process for the preparation of a solid formulation according to the invention.

In the practical preparation of the solid formulations according to the invention i. a. commercial products are used, which may additionally contain solvents, such as water, and other additives, preferably using high concentrates. In particular, lower amounts of inorganic substances, especially inorganic salts, may be included in the products used. For example, higher molecular weight sulfonates can be produced by up to 20% by weight of inorganic salts, in particular inorganic alkali metal salts, eg. For example, sodium sulfate. All quantitative data, such as parts by weight and weight ratios, in particular to the polyalkoxylates according to the invention and higher molecular weight sulfonates, refer to the named constituents and are to be converted when using such commercial products according to the actual content of the product of said constituents.

According to the invention, the preparation of the solid formulations can be carried out by removing fluid from a fluid-containing mixture comprising at least a portion of the ingredients and removing the solid which has been at least partially freed from the fluid. winnt. If necessary, the remaining ingredients may be presented prior to removal of the fluid and / or added after removal of the fluid. The template is preferably carried out as a solid. If the addition takes place as a further fluid-containing mixture, fluid is removed again and the solid which is at least partially freed from the fluid is recovered. The fluid is preferably a solvent for one or more ingredients, especially water. As part of a multi-stage process, various fluids can be used.

In a preferred embodiment, the fluid-containing mixture comprises at least part of components (a) and (b). In general, it is even expedient for such a fluid-containing mixture to contain the total amount of components (a) and (b).

According to the invention, the preparation of the formulation is preferably carried out by removing the fluid as quickly as possible, ie in particular by drying as quickly as possible, the processes which can be used being known in principle from the prior art. The removal of fluid is hereinafter referred to as "drying." It is important that the removal of the fluid in local (molecular to supermolecular) scale of size proceeds rapidly enough, which contributes to the formation of the solids according to the invention On the other hand, as far as the optional starting materials permit and practical considerations make this desirable, it can be comparatively slow, for example by sequentially applying a large number of very thin fluidized or fluidized bed layers, each of which is rapidly dried by itself.

According to the invention, fluid should be withdrawn up to or slightly above the point at which solids according to the invention are formed. Substantially more extensive removal of the fluid is basically possible, but not always expedient, since, according to experience, too low a residual moisture can impair the mechanical stability and solubility properties of many granules ("dry-drying"), without any restriction to the theory, it is assumed in principle If drying is too extensive, unwanted rearrangement and cross-linking reactions within the granules may occur.The degree of drying which is ideal for a particular process product is due to the complexity of the system of many factors (including the desired properties and the intended use of the granules, the composition of the registered material, in the practical implementation most favorable process parameters, etc.) dependent and largely empirical to determine.

According to a preferred embodiment of the invention, the removal of the fluid by convection drying takes place. In this case, methods are preferred in which the material to be dried is sprayed in a fluid or pasty state. This includes, in particular, spray drying, in which a fluid-containing material is sprayed (entry), fluid is removed in the gas stream, and the material which has been partially or completely freed from the fluid is recovered as a particulate discharge. The spray processes also include fluidized bed processes in which a solid, preferably particulate material is presented ("receiver"), a fluid-containing material is sprayed ("entry"), fluid is removed in the gas stream, whereby initially introduced particulate material and sprayed material with each other associate and the partially or completely freed from the fluid material in association with the submitted particulate material as a particulate "discharge" wins.

Another suitable drying method is freeze-drying (Method C). This method is also familiar to the person skilled in the art.

The respective process product, usually the discharge, can be used directly according to the invention or in turn can be used as a template in further process steps for the preparation of the particular application form.

In a particular embodiment of the invention, the drying is carried out by spray-drying, e.g. using a so-called spray tower (method A).

In a specific embodiment of Process A, solid formulations according to the invention, e.g. water-soluble granules (SGs), from the components (a), (b) and optionally (c) prepared by mixing suitable fluid-containing mixtures of (a), (b) and optionally (c), e.g. aqueous concentrates, spray-dried (method A1). Preferably, the product discharge takes place here continuously.

If a component (b2) is used, it can be added as a fluid-containing slurry or dispersion to the mixtures of components (a), (b1) and optionally (c) before spray drying (so-called Co - spray drying). Ingredients which are attributable to component (d) are in many cases incorporated together with the other components, for example in the form of commercial products.

In a further particular embodiment of the invention, the drying takes place in the fluidized bed or fluidized bed process (process B).

In the fluidized bed or fluidized bed process, the product is preferably discharged batchwise (batch or batch process.) For the application of the process, it is generally necessary to provide a suitable particulate material (carrier nuclei) to which the actual entry Depending on the setup and control of the process, a single, few, or many layers may be applied to the cores, taking into account that each one may be applied to the cores Due to the complexity of the system, the choice of the number and thickness of the layers is due to many factors (including, for example, desired properties and use of the granules, composition of the material introduced , in the practical implementation cheapest Proz Ess parameter etc.) dependent and largely empirical to determine.

In a specific embodiment of Process B, solid formulations of the invention, e.g. water-soluble SGs, prepared by initially introducing component (d) -based particulate material (carrier nuclei) and mixing components (a), (b) and optionally (c) in the form of one or more fluid-containing mixtures, e.g. as aqueous concentrate (s) (method B1).

In principle, the present invention relates to the use of a high molecular weight sulfonate as a solid carrier of liquid or low melting polyalkoxylate in solid formulations.

The solid formulations according to the invention are used in particular as an additive to a composition containing phytochemicals or as a solid carrier therefor. Thus, the solid formulations according to the invention, for example, as a basis for the production of crop protection agents, for example in a Fluidized bed granulation process, or be used as stand-alone products according to the invention, for example, in Tankmixverfahren be used as a potentiating additive to pesticides. There, they serve as effectuating auxiliaries ("boosters") for the plant protection active substance (s) contained in the composition, a further subject of the present invention is therefore the use of a solid formulation according to the invention for increasing the efficacy of plant protection active ingredients.

Likewise, the formulations according to the invention can be used in the field of wood preservatives. Here, too, the solid formulations according to the invention are dissolved in the tank mix and used in so-called temporary wood preservation or in the boiler pressure process. It is generally important to keep the wood preservatives active. This applies in particular to dip tank mixes, the polyalkoxylates improving the penetration of the active ingredients into the wood. SG formulations then deliver z. B. dissolved in water preferably also called microemulsions, which are particularly preferred in wood preservation.

The present invention will now be further described by the following non-limiting examples.

Examples 1 to 37: solid formulations

A series of solid formulations according to the methods V1, V2, V3 or

V4 made and rated.

Method V1: Preparation by freeze-drying

The respective ingredients were added in a 250 ml round bottom flask with stirring at RT or by gentle warming to 50 ° C with water and dissolved. Subsequently, the round bottom flask was placed in a bath of dry ice and acetone and the mixture froze at about -70 to -78 ° C to a solid mass. Alternatively, liquid nitrogen or liquid air was used for freezing. The freezing lasted usually only a few minutes.

Then the flasks were connected to a conventional freeze dryer. Depending on the amount, the freeze-drying process took up to 48 hours, with a typical negative pressure below 0.5 mbar. The residues were isolated from the flasks, ie generally scraped out with a spatula and subsequently evaluated in terms of their properties.

Method V2: Preparation by evaporation The ingredients are dissolved in water and a portion of this amount in about 1 - 2 mm layer height in a Petri dish. The Petri dish is placed on a hot plate to constant weight and dried at 100 ° C, the aqueous mixture by free evaporation of water at atmospheric pressure.

Method V3: Preparation by means of rotary evaporation

The ingredients are dissolved in water and evaporated on a rotary evaporator at 60 ° C and 100 to about 50 mbar.

Table 1 below shows information on ingredients, quantities, production processes and evaluation for some formulations.

Table 1 :

1) Reviews of consistency:

S-O: good properties, solid powder when scratching or regurgitation with a

Spatula remain firm and crumbly and not prone to greasy effects.

S-1: almost does not smear when scratched with the spatula;

S-2: smears very easily when scratched with a spatula;

S-3 lubricates significantly when subjected to mechanical stress or scratching;

S-4 the freeze-dried mass is already viscous and very greasy;

²⁾ Hygroscopicity indicated in wt.% - Water absorption at relative humidity of 50% or 65% (the determination was carried out in each case up to the saturation value, ie constant weight, whereby the weight increase of 1 g samples in small Petri dishes was determined up to 4 weeks) 3) Total amount of ingredients dissolved in water

4) amount of ingredient / amount of water

Amount of water in which the ingredients were dissolved

Method V4: Preparation by means of spray drying

The ingredients were dissolved in water and subjected to the conditions given in the following Table 2 in a spray tower made by Niro-Reiholb (disc tower, height: 6 m, diameter: 1 m, two-fluid nozzle with cyclic gas system, cyclone and filter system, use of nitrogen; Jet gas mass flow: 1 1.5 kg / h, die gas pres- sure: 2.7 bar, product inlet temperature 20 ° C) spray-dried.

Table 2

^* ) Failed attempt; no product discharge; about 50 kg of powder in the filter.

The residual moistures of the solid formulations obtained were 2.1% (Example 33), 1.7% (Example 34) and 1.5% (Example 36). Table 3 below is an overview of the ingredients used.

Table 3

Without being bound by theory, the following mechanism is proposed to explain the observation that higher molecular weight sulfonates having high and equal weight or equal proportions of polyalkoxylates provide solid powders in spray-drying or freeze-drying:

In both cases, both in the spray and the freeze-drying, the pre-concentrates, the solvent, generally water, withdrawn quickly and / or relatively gently. It may be assumed that initially associates exist or form, characterized in that in addition to dipole-dipole and van der Waals interactions also so-called "template" effects (ie favoring and / or changing the incorporation of macromolecules in preformed supra-molecular aggregation due to cooperative effects, similar to the processes known in the formation of many biological macromolecular structures), in which the cation of the sulfonate interacts with the polyalkoxylate chain to form chelate-like structures. or macromeric anions with comparatively high stability.

It is generally known that large and / or macromeric fragile anions with many degrees of freedom of spatial orientation, i. H. low rigidity of the molecule, often only with equally large and / or macromeric cations stable lattice or solids with crystal-like structure and / or associates can form with melting points above 50 ° C. When viewed microscopically, these scaffold associates remain in the inventive, fast or gentle, kinetically controlled solvent removal. Macroscopically, this process ultimately yields loose powders or granules, typically with air fractions of at least 20% by volume and bulk densities between 0.3 and 0.9 g / ml.

In contrast, the slow or non-gentle removal of the solvent from mixtures according to the invention, as it is known for example from US Pat. B. in a rotary evaporator, with dissolution of the molecular associates at thermodynamic Control to films or pasty masses of higher density (> 0.9 g / ml), which are no longer dosed and less suitable for the production of pesticides.

The proposed mechanism is presented for the purpose of illustrating the invention and does not limit it.

Examples 38: Use of a solid-form formulation according to the invention for the production of an epoxiconazole-based crop protection agent by means of a fluidized bed

Epoxiconazole SC:

1.5 kg SC were prepared according to EP 707 445 B1 by grinding an aqueous mixture with 12.5% epoxiconazole, 5% Wettol LF 700, 2.5% Tamol NH 7519 and 0.1% silicone SRE (antifoam agent) in one Laboratory ball mill produced, with a particle distribution of 80% <2 microns were obtained.

Method V5: Production by fluidized bed

A WSG laboratory plant (model Turbojet) of the company Hüttlin becomes at 70 ° C with approx. 80 in the ³

Nitrogen stream with 1, 5 kg of the solid formulation of Example 33 fluidized. Afterwards, 2.5 kg of epoxiconazole SC are sprayed over the three bottom nozzles of the system within 45 minutes, a coarse-grained granule with good dispersing properties being obtained.

Granulate output calculated 2.0 kg; found about 1, 9 kg with an active ingredient content of about 19% Epoxicoanzol and 38% additive (Wettol LF 700).

The solid formulations according to the invention are dust-free, fast-wetting, readily dispersible, non-hygroscopic or hardly hygroscopic granule formulations having good storage stability. This also applies to the pesticides produced therefrom.

Claims

claims:

A solid formulation comprising: a) liquid or low melting polyalkoxylate; and b) a carrier based on high molecular weight sulfonate, wherein

(i) the proportion of liquid or low melting polyalkoxylate relative to the total weight of the solid formulation is at least 15% by weight; (ii) the proportion of liquid or low melting polyalkoxylate relative to the total weight of the higher molecular weight sulfonates is at least 30% by weight; and

2. A solid formulation according to claim 1, wherein the polyalkoxylate is selected from optionally end-group-modified alkoxylated fatty alcohols, alko xylierten fatty acid esters, alkoxylated fatty amines, alkoxylated glycerides, alkoxylated sorbitan esters, alkoxylated alkylphenols and alkoxylated di- and tristyrylphenols with alkoxylate.

3. The solid formulation according to claim 1, wherein the polyalkoxylate is selected from alcohol polyalkoxylates of the formula (I)

R ⁷ -O- (C _m H _2m O) _x - (C _n H _2n O) _y - (C _p H _2p O) _z -R ⁶ (I)

wherein

R ^{6 is} an organic radical;

R ^{7 is} an aliphatic hydrocarbon radical having 3 to 100 carbon atoms;

m, n, p are independently an integer from 2 to 6, preferably from 2, 3, 4 or 5; x, y, z independently represent a number from 0 to 1000; and

x + y + z corresponds to a value of 2 to 1000.

4. A solid formulation according to claim 3, wherein R ^{7 is} branched or linear, C _3-3 o-alkyl, preferably C ₅ -C ₂₄ alkyl, or C _3-3 o-alkenyl, preferably C ₅ -C ₂₄ alkenyl, stands.

5. A solid formulation according to any one of claims 1 to 4, wherein the formulation contains at least 20 wt .-%, preferably at least 25 wt .-% and in particular at least 30 wt .-% alkoxylate.

6. A solid formulation according to any one of claims 1 to 5, wherein the formulation at most 70 wt .-%, preferably at most 60 wt .-% and in particular at most 45 wt .-%. Contains alkoxylate.

A solid formulation according to any one of claims 1 to 6, wherein the higher molecular weight sulfonate has a weight average molecular weight of at least 1 kDa, preferably at least 2.5 kDa, and more preferably at least 5 kDa.

8. A solid formulation according to any one of claims 1 to 7, wherein the higher molecular weight sulfonate is a lignosulfonate.

9. A solid formulation according to any one of claims 1 to 7, wherein the higher molecular weight sulfonate is a condensation product based on a sulfonated aromatic, an aldehyde and / or ketone, and optionally a compound selected from uncharged aromatics, urea and urea derivatives.

10. A solid formulation according to claim 9, wherein the condensation product repeating units having the structure of the formula (IIa) and / or formula (IIb)

and / or formula (Mc)

which comprises

R ^{8 is} hydrogen, one or more hydroxyl groups or one or more d-β-alkyl radicals;

q1 corresponds to a value of 100 to 10 10; and

A is methylene, 1, 1-ethylene or a group of the formulas

-CH ₂ -NH-CO-NH-CH ₂ -, -CH-NH-CO-NH-CH-

CH, CH, stands.

1. A solid formulation according to claim 9, wherein the condensation product repeating units having the structure of the formula (III): which comprises

R ^{9 is} hydrogen, one or more hydroxyl groups or one or more Ci-β-alkyl radicals; q2 corresponds to a value of 100 to 10 ¹⁰ ;

A is methylene, 1, 1-ethylene or a group of the formulas

-CH ₂ -NH-CO-NH-CH ₂ -, -CH-NH-CO-NH-CH-

I i

CH ₃ CH ₃ is.

12. A solid formulation according to any one of claims 1 to 7, wherein the higher molecular weight sulfonate is a copolymer wherein the copolymer constituting monomers M α) at least one monoethylenically unsaturated monomer M1 having at least one sulfonic acid group, and ß) at least one neutral, monoethylenically unsaturated Include monomer M2.

13. A solid formulation according to any one of claims 1 to 12, wherein the sulfonate is an ammonium, alkali metal, alkaline earth metal or transition metal sulfonate.

14. The solid formulation according to any one of claims 1 to 13, wherein the formulation at least 15 wt .-%, preferably at least 25 wt .-% and in particular at least 30 wt .-%. contains higher molecular weight sulfonate.

15. A solid formulation according to any one of claims 1 to 14, wherein the formulation at most 80 wt .-%, preferably at most 70 wt .-% and in particular at most 55 wt .-%. contains higher molecular weight sulfonate.

16. A solid formulation according to any one of claims 1 to 15, wherein the weight ratio of liquid or low melting polyalkoxylate to higher molecular weight sulfonate is at most 2: 1.

17. A solid formulation according to any one of claims 1 to 16, wherein the weight ratio of liquid or low melting polyalkoxylate to higher molecular weight sulfonate is at least 3:10.

18. A solid formulation according to any one of claims 1 to 17, wherein component (b) b1) higher molecular weight sulfonate; and b2) inorganic solid.

The solid formulation of claim 18, wherein the inorganic solid is sparingly soluble or insoluble in water.

20. A solid formulation according to claim 18 or 19, wherein the inorganic solid is selected from alumina-based substances, in particular aluminum oxide and bauxite, silicon dioxide-based substances, in particular silicates and silicate minerals, especially diatomaceous earths (kieselguhr, diatomite), silicas, pyrophyllite, talc, mica and clays such as kaolinite, bentonite, montmorillonite and attapulgite.

21. The solid formulation according to claim 20, wherein the total inorganic solids in the formulation is less than 15% by weight, in particular less than 10% by weight and particularly preferably less than 5% by weight.

22. A solid formulation according to any one of claims 18 to 21, wherein the weight ratio of higher molecular weight sulfonate to inorganic solid is at least 2, preferably at least 5 and in particular at least 10.

A solid formulation according to any one of claims 1 to 22, further comprising: c) further adjuvant.

24. A solid formulation according to claim 23, wherein the further auxiliaries is selected from c1) surface-active auxiliaries; c2) anti-settling agents, anti-foaming agents, retention aids, pH buffers, anti-drip agents and other auxiliaries to improve the handling and / or physical properties of the formulation; c3) chelating agents.

25. A solid formulation according to claim 23 or 24, wherein the formulation at most 60 wt .-%, preferably at most 55 wt .-% and in particular at most 50 wt .-%. contains further excipient.

The solid formulation according to any one of claims 1 to 25, further comprising: d) water-soluble inorganic salt.

A solid formulation according to claim 26, wherein the inorganic salt is ammonium sulfate.

A solid formulation according to any one of claims 1 to 27 which is substantially anhydrous.

29. A solid formulation according to any one of claims 1 to 28, namely a granulate.

30. A solid formulation according to claim 29, wherein the granules are a water-dispersible granules (WG or a water-soluble granules (SG)).

31. A solid formulation according to claim 29 or 30, wherein the granulate is a fluidized bed granulate (WSG).

32. A solid formulation according to any one of claims 1 to 27, namely a powder.

33. The solid formulation of claim 32, wherein the powder is a dry flowable powder (DF).

34. Use of a high molecular weight sulfonate as a solid carrier of liquid or low melting polyalkoxylate in solid compositions.

35. A process for preparing a solid formulation according to any one of claims 1 to 33, wherein fluid is removed from a fluid mixture containing at least a portion of the ingredients and wins the fluid at least partially freed from the fluid.

36. The method of claim 35, wherein the fluid is water.

37. The method of claim 35 or 36, wherein the fluid is removed by freeze-drying or spray-drying.

38. The method according to claim 35 or 36, wherein initially introduced on the inorganic salt component (d) based particulate material, at least a part of components (a) and (b) enters as a fluid-containing mixture, fluid fluidized bed process and at least removed from the fluid partially freed and the particulate material comprising inorganic salt component (d) is recovered.

39. Use of a solid formulation according to any one of claims 1 to 33 as an additive to a plant protection active ingredient-containing composition.

40. Use of a solid formulation according to any one of claims 1 to 33 as a solid carrier for a plant protection agent-containing composition.