Conjugates of polysaccharides and hydrophobic compounds as emulsion stabilizers

Abstract

The invention relates to a conjugate of a sugar compound selected from the group consisting of disaccharides, oligosaccharides and polysaccharides and at least one hydrophobic compound selected from the group consisting of terpenes, polyterpenes and polyterpene ethers, in which the hydrophobic compound in the conjugate is bound directly to the oxygen atom of the sugar or is present as a group of formula (I) or (II): R-O-(Y) k-A1-X1-(I) R-O-(Y) k-A1-X2-A2-X3-(II), wherein in the formulae (I) and (II), R is a group of a terpene compound, a polyterpene or a polyterpene ether compound, k is 0 or 1, Y is C (O) or C (O) NH, A1 is a direct bond or a C1-C6 alkylene group, A2 is a C2-C10 alkylene group, X1 is C (O), or if k = 1 and A1 is a C1-C6 alkylene group, may also be OC (O) or NHC (O), and wherein X1 is attached to the oxygen atom of the sugar compound, 20X2 is C (O) NH or NHC (O) NH, X3 is N = or NH-, and X3 is N = or NH-. And wherein X3 in formula (II) is attached to the carbon atom of the sugar compound. The invention also relates to the use of such a conjugate as a stabilizer for aqueous emulsions of liquids immiscible with water.

Description

[0001] The present invention relates to conjugates of polysaccharides and hydrophobic compounds and their use as stabilizers for aqueous emulsions of water-immiscible liquids, in particular emulsions of water-immiscible liquids, which aqueous emulsions contain organic active substances, in particular agrochemical compounds or cosmetic compounds. The present invention also relates to an aqueous composition of an organic active compound, in particular an agrochemical compound, which aqueous composition is an aqueous emulsion of a water-immiscible liquid containing the at least one organic active substance, wherein the aqueous emulsion contains at least one conjugate as defined herein. Background Art

[0002] Aqueous emulsions play an important role in many daily processes such as washing and cleaning processes, in the formulation and application of active ingredients in crop protection, pharmaceuticals and cosmetics, and in industrial processes involving aqueous emulsions. An emulsion is known to be a fine dispersion mixture of an aqueous liquid and a liquid that is immiscible or only very slightly miscible with water, wherein one of the two liquid phases is present as a dispersed phase or internal phase distributed in the other phase. If the dispersed phase is the aqueous phase, it is called a water-in-oil emulsion (w / o emulsion), while if the water-immiscible liquid forms the dispersed phase, it is called an oil-in-water emulsion (o / w emulsion). Due to the high surface energy, emulsions are thermodynamically and kinetically unstable, wherein the dispersed phase tends to coalesce into larger phases to reduce the surface energy. Therefore, surface-active substances are used to stabilize aqueous emulsions.

[0003] Many active ingredient formulations are emulsions or form emulsions when diluted with water. For example, agricultural active compounds must be formulated in a manner that allows for safe and efficient application of the agricultural active compounds. For this purpose, the active compounds are usually sold in concentrated formulations, which are diluted in water during their application. Surfactants play a key role in such formulations. On the one hand, they ensure problem-free dilution in water without emulsion stratification or sedimentation and uniform distribution in the aqueous phase, and at the same time stabilize the finely distributed active ingredients in the aqueous diluent. Similar requirements must be met in pharmaceutical compositions.

[0004] In cosmetic and pharmaceutical formulations such as creams and ointments, it is often necessary to co-formulate water-insoluble liquids with the aqueous phase.

[0005] In detergents and cleaners, surfactants are required to separate dirt, especially grease and oily contaminants, from the soiled surface and stabilize them in the aqueous cleaning phase (such as laundry washing foam or rinse liquid).

[0006] Although surfactants are essential for many applications, the following problems still arise: Conventional surfactants can affect the environment even when used as prescribed, because most of them are only slowly degraded. Therefore, there is a basic need for surfactants that are readily biodegradable.

[0007] M-H. Alvès et al., Biomacromolecules 2014, 15, 242-251 describe amphiphilic polymers having a dextran backbone and thio-functionalized terpene groups attached to the backbone. The amphiphilic polymers can be used to prepare o / w fine emulsions. However, these amphiphilic polymers are difficult to prepare and are limited to terpenes having free double bonds. Their properties are not entirely satisfactory, and due to the presence of sulfur, the polymers may produce toxic degradation products.

[0008] For several reasons, such as delayed release, toxicity, volatility, degradation or compatibility with other active substances, organic active substances can be formulated as microcapsule formulations, such as microcapsule suspensions. In such formulations, the organic active compound is provided in the form of particles, where the organic active compound or a solution of the organic active compound in a water-immiscible solvent is encapsulated or embedded by a shell of a water-insoluble polymer (see H. Mollet, A. Grubenmann “Formulation Technology” 1st edition, Wiley-VCH Verlag GmbH, Weinheim 2001, Chapters 6.4 and 14.2.2). Such polymers can be, for example, polyurethanes, polyureas, polyamides, polyesters, polycarbonates, urea / formaldehyde resins, melamine / formaldehyde resins, polystyrenes, or acrylate polymers. Although the microencapsulation of organic active substances provides considerable benefits since it reduces the acute toxicity and phytotoxicity of the organic active substance or reduces its volatility and degradation, it is generally difficult to achieve. In particular, aggregation of the organic active substance during or after encapsulation is a major problem if an encapsulation method that may work for a specific organic active compound does not necessarily work for another organic active compound. Another problem associated with microcapsule formulations is the massive release of microplastics into the environment. In the environment, microplastics can accumulate in animals or plants and thus ultimately enter human nutrition (see, for example, C. M. Rochmann, “The global odyssey of plastic pollution”, Science 368 (2020) pages 1184 - 1185). Therefore, the use of synthetic polymer microcapsules increasingly suffers from ecological concerns on the part of consumers and regulatory authorities. Accordingly, there is a need to provide delivery forms for organic active substances that can be produced without or with a reduced amount of non-degradable plastic materials. Summary of the Invention

[0009] It has now surprisingly been found that the above-mentioned problems are solved or at least improved by conjugates of sugar compounds selected from disaccharides, oligosaccharides and polysaccharides and at least one hydrophobic compound selected from terpenes, polyterpenes and polyterpene ethers. When the conjugate is present in an aqueous emulsion of a water-immiscible liquid, in particular an oil-in-water emulsion (hereinafter o / w emulsion), the stability of the emulsion is significantly improved and the emulsion can remain stable for at least several weeks. Microscopic analysis of the emulsion shows that the conjugate molecules aggregate at the phase boundary and thus form a stable layer surrounding the droplets present in the aqueous emulsion, regardless of whether the emulsion is an oil-in-water (o / w) emulsion and the droplets are formed from a water-immiscible liquid or the emulsion is a water-in-oil (w / o) emulsion and the droplets are formed from water emulsified in a non-aqueous liquid. The formation of the stable layer is observed regardless of whether the water-immiscible liquid contains a solid organic active substance dissolved in a water-immiscible solvent.

[0010] The presence of the conjugate in the aqueous emulsion of the water-immiscible liquid stabilizes the droplets against coalescence and Ostwald’s ripening and thus against phase separation. In addition, the conjugate molecules promote the emulsification of the non-aqueous phase in the aqueous phase and vice versa.

[0011] Accordingly, a first aspect of the present invention relates to conjugates as described herein. These conjugates are formed from a sugar compound selected from disaccharides, oligosaccharides and polysaccharides and at least one hydrophobic compound selected from terpenes, polyterpenes and polyterpene ethers, the hydrophobic compound being directly (i.e., covalently) bound to an oxygen atom of the sugar compound or being present as a group of formula (I) or (II):

[0012] R-O-(Y) k -A 1 -X 1 -(I)

[0013] R-O-(Y) k -A 1 -X 2 -A 2 -X 3 -(II)

[0014] wherein in formula (I) and (II)

[0015] R is a group of a terpene compound, a polyterpene or a polyterpene ether compound

[0016] k is 0 or 1,

[0017] Y is C(O) or C(O)NH,

[0018] A 1 is a direct bond or a C1-C6 alkylene group,

[0019] A2 is a C2-C 10 alkylene group,

[0020] X 1 is C(O), or, if k = 1 and A 1 is a C1-C6 alkylene group, may also be OC(O) or NHC(O), and wherein X 1 is attached to the oxygen atom of the polysaccharide,

[0021] X 2 is C(O)NH or NHC(O)NH,

[0022] X 3 - is N= or NH-,

[0023] and wherein X in formula (II) 3 is attached to the carbon atom of the sugar compound.

[0024] The conjugates of the present invention are particularly useful for stabilizing aqueous emulsions of water-immiscible liquids, especially oil-in-water emulsions.

[0025] Accordingly, a second aspect of the present invention relates to the use of the conjugates of the present invention as stabilizers for aqueous emulsions of water-immiscible liquids, especially oil-in-water emulsions, and a method for stabilizing an aqueous emulsion of a water-immiscible liquid, especially an oil-in-water emulsion, the method comprising incorporating a conjugate of a sugar compound and at least one hydrophobic compound as described herein into the aqueous emulsion of the water-immiscible liquid. Specific groups of embodiments of the second aspect of the present invention relate to use methods for stabilizing o / w emulsions containing at least one organic active compound, such as an organic active compound selected from agrochemicals, aroma chemicals, pharmaceutically active compounds, vitamins, cosmetic active substances, and organic effect compounds.

[0026] However, a further aspect of the present invention relates to

[0027] - an aqueous composition which is an aqueous emulsion of a water-immiscible liquid, the aqueous emulsion containing at least one conjugate of the present invention;

[0028] - an aqueous composition of an organic active compound which is an aqueous emulsion of a water-immiscible liquid, the aqueous emulsion containing at least one conjugate of the present invention, wherein the water-immiscible liquid contains the organic active compound of the present invention;

[0029] - a method for controlling phytopathogenic organisms, the method comprising the step of applying a pesticidally effective amount of the aqueous composition as defined herein and hereinafter;

[0030] - a washing and cleaning composition containing a conjugate of the present invention.

[0031] The present invention has several advantages. The conjugates described herein promote the emulsification of a non-aqueous phase in an aqueous phase and stabilize the droplets of the emulsion against Ostwald ripening and coalescence and thus against phase separation. Accordingly, other emulsifiers that are typically required to stabilize emulsions can be avoided or at least their amount can be reduced. In addition, the conjugates of the present invention can be prepared in good yields by standard synthetic techniques of organic chemistry or polymer chemistry, respectively.

[0032] As mentioned above, the conjugate molecules aggregate at the interface between the aqueous and non-aqueous phases of the emulsion and form a stabilizing layer that stabilizes the droplets against coalescence and thus against phase separation. In the case of an o / w emulsion, the conjugate molecules form a stabilizing layer surrounding the oil droplets present in the o / w emulsion, regardless of whether the water-immiscible liquid itself forms oil droplets or contains one or more organic active compounds (such as a biocide) that form droplets dissolved in the water-immiscible solvent. In the case of a reverse emulsion, i.e., in the case of a w / o emulsion, the conjugate molecules form a stabilizing layer surrounding the aqueous droplets present in the w / o emulsion, which aqueous droplets may contain a water-soluble biocide dissolved in the aqueous phase. Accordingly, the conjugate molecules mimic the encapsulation of the biocide compound. For example, the presence of the conjugate in an aqueous emulsion of a biocide compound will stabilize the emulsion droplets, thereby increasing the stability of the emulsion. At the same time, they provide good compatibility with other biocides in the aqueous emulsion. In addition, improved selectivity of the biocide for the target organism can be achieved through the conjugate. Since the conjugate molecules contain carbohydrate groups, they will be biodegradable in the environment. Similarly, terpenes, polyterpenes, and polyterpene ethers of biological origin will be biodegradable under environmental conditions. Accordingly, the conjugates are eligible as biodegradable surfactants. In addition, it has been found that the conjugates provide benefits similar to those of conventional microencapsulation. Accordingly, they can replace conventional microencapsulation materials and thus reduce the input of microplastics into the environment. Detailed Description

[0033] The term "conjugate of a polysaccharide and at least one hydrophobic compound" should be understood to mean a polysaccharide molecule bearing at least one hydrophobic molecule selected from terpenes, polyterpenes, and polyterpene ethers, wherein the hydrophobic compound is directly bound to the sugar compound, i.e., covalently bound to a carbon or oxygen atom of the sugar compound by a covalent bond, or the hydrophobic compound is bound through a covalent linking group that together with the hydrophobic compound forms a group having formula (I) or (II), respectively.

[0034] Herein and throughout this application, the terms "organic active compound", "organic active substance" and "active compound" are used synonymously. These terms are understood by those skilled in the art to mean organic chemical compounds that trigger physiological effects in living organisms and plants, as well as substances that cause chemical effects or catalyze chemical reactions in the inanimate nature. Examples of active substances are aromatic chemicals, organic crop protection agents, organic pharmaceuticals, organic cosmetic active substances and organic active substances for use in the construction sector, called construction chemicals, in particular catalysts for products used in the construction sector, such as crosslinking or polymerization catalysts. The term "organic active substance" also includes "organometallic active substances".

[0035] Herein and hereinafter, the term "immiscible with water" refers to a material whose solubility in deionized water at 20 °C and 1 bar is at most 5 g / L, especially at most 1 g / L. Under the conditions given herein, the solubility of a material immiscible with water in deionized water can be zero, i.e., below the detection limit. Herein and throughout this specification, the terms "liquid immiscible with water" and "organic liquid immiscible with water" are used synonymously.

[0036] The term liquid refers to a material that is in the liquid state under ambient conditions, i.e., neither solid nor gaseous. In the context of the present invention, the liquid material preferably has a dynamic viscosity in the range from 0.2 to 2000 mPas at 20 °C, especially in the range from 0.5 to 1000 mPas. Herein and throughout this specification, ambient conditions refer to a temperature in the range from 20 °C to 25 °C and atmospheric pressure, i.e., approximately 1 bar.

[0037] The term "low molecular weight organic active compound" refers to an organic or organometallic chemically active compound having a defined molecular weight Mn, which is generally below 1000 daltons and typically in the range from 80 to <1000 daltons and especially in the range from 100 to 500 daltons. The molecular weight can be determined by mass spectrometry.

[0038] The term "sensitive active substance" refers to an organic active compound that is unstable to the conditions of its environment and is damaged or deteriorated, for example, due to the pH of its environment or by oxidation.

[0039] The terms "organic crop protection agent", "agrochemical", "agrochemical compound", "pesticide" and "pesticide compound" are used synonymously and refer to any physiologically active compound suitable for agricultural purposes. In particular, it means a compound suitable for controlling phytopathogenic organisms, such as harmful plants, volunteer plants, phytopathogenic fungi, phytopathogenic arthropods (such as phytopathogenic insects and arachnids), phytopathogenic nematodes and molluscs. Thus, the term "agrochemical compound" includes herbicides, fungicides, insecticides, nematicides and molluscicides. The term "agrochemical compound" also includes plant growth regulators, i.e., compounds that slow down or reduce the growth of crop plants, and herbicide safeners, i.e., compounds that reduce the phytotoxic effect of herbicides on crop plants.

[0040] With respect to agrochemical compounds, the term "water-insoluble or slightly water-soluble" means that the agrochemical compound is insoluble in deionized water, i.e., its solubility in deionized water is less than 0.1 g / L, or it has a solubility of not more than 5 g / l or not more than 3 g / l, especially not more than 2 g / l, for example 0.1 to 5 g / l, especially 0.1 mg / l to 3 g / l or 0.1 mg / l to 2 g / l. The values given here refer to the solubility of the pesticide in deionized water as determined at 20 °C and 1 bar. In this context, the term "water-soluble" means that the pesticide is soluble in deionized water, i.e., its solubility in deionized water is at least higher than 5 g / l, especially at least 10 g / l, particularly at least 20 g / l, as determined at 20 °C and 1 bar. Water-soluble pesticide compounds can also be completely miscible with deionized water at 20 °C and 1 bar.

[0041] The term "alkyl" refers to having, for example, 1 to 40 carbon atoms (C1-C 40 alkyl), especially 1 to 20 carbon atoms (C1-C 20 alkyl), or 8 to 40 carbon atoms (C8-C 40 alkyl), or 8 to 20 carbon atoms (C8-C 20a monovalent, straight-chain or branched-chain saturated hydrocarbon group having from 1 to 4 carbon atoms (C1-C4 alkyl). Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, 3,7-dimethyloctan-1-yl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, and, in the case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, their isomers. Examples of C1-C4-alkyl are, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl. The term "alkyl" also includes saturated hydrocarbon groups produced by the oligomerization of C2-C4 olefins such as ethylene, propylene, 1-butene and isobutene. These groups will generally have from 6 to 40 carbon atoms and be a mixture of different isomers.

[0042] The term "alkylene" refers to having, for example, from 2 to 40 carbon atoms (C2-C 40 alkylene), in particular from 2 to 20 carbon atoms (C2-C 20 alkylene), or from 8 to 40 carbon atoms (C8-C 40 alkylene), or from 8 to 20 carbon atoms (C8-C 20 alkylene) or from 2 to 10 carbon atoms (C2-C 10A divalent, straight-chain or branched-chain saturated hydrocarbon group of (alkylene). Examples of alkylene include, but are not limited to, 1,2-ethanediyl, 1,2- or 1,3-propanediyl, 1,4-butanediyl, 2-methylpropane-1,3-diyl, 1,1-dimethylethane-1,2-diyl, 1,5-pentanediyl, 1,6-hexanediyl, 2,2-dimethylpropane-1,3-diyl, 1,2-octanediyl, 1,8-octanediyl, 1,10-decanediyl, 3,7-dimethyloctane-1,7-diyl and 3,7-dimethyloctane-1,8-diyl.

[0043] The term "alkenyl" refers to a monovalent, straight-chain or branched-chain ethylenically unsaturated hydrocarbon group having, for example, 2 to 40 carbon atoms (C2-C 40 alkenyl), particularly 2 to 20 carbon atoms (C2-C 20 alkenyl), or 8 to 40 carbon atoms (C8-C 40 alkyl), or 8 to 20 carbon atoms (C8-C 20 alkenyl) or 2 to 4 carbon atoms (C2-C4 alkenyl) and having at least one, for example 1, 2 or 3 ethylenic unsaturated double bonds. Examples of alkenyl include, but are not limited to, vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, isotridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl and, in the case of nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, isotridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, as their isomers, for example decenyl isomers 3,7-dimethyloct-6-en-1-yl and 2,6-dimethyl-2,6-octadien-8-yl.

[0044] The term "cycloalkyl" refers to a saturated cycloaliphatic hydrocarbon group having, for example, 3 to 10 carbon atoms (C3-C 10 cycloalkyl) or 5 to 8 carbon atoms (C5-C8 cycloalkyl). Examples of cycloalkyl include, but are not limited to, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl and cyclohexadecyl.

[0045] The terms "bicycloalkyl" and "tricycloalkyl" refer to saturated bicyclic and tricyclic hydrocarbon groups. "Bicycloalkyl" generally has 6 to 12 carbon atoms (C6-C 12bicycloalkyl), while "tricycloalkyl" typically has 8 to 12 carbon atoms. Examples of bicycloalkyl and tricycloalkyl include, but are not limited to, norbornyl (=bicyclo[2.2.1]heptyl), isobornyl (=1,7,7-trimethylbicyclo[2.2.1]heptyl), decahydronaphthyl (=bicyclo[4,4,0]decyl), and adamantyl (tricyclo[3.3.1.1 3.7 decyl).

[0046] Herein and throughout this specification, the terms "wt.-%" and "% by weight" have the same meaning.

[0047] "Molecular weight Mn" or "molar mass Mn" is the number-average molecular weight or molar mass. "Molecular weight Mw" or "molar mass Mw" is the weight-average molecular weight or molar mass. Unless otherwise stated, Mn and Mw are determined by size-exclusion chromatography (SEC), which is carried out by a standard method similar to that disclosed in the art, using, for example, a polyester copolymer as the stationary phase, dimethylformamide + 0.5% LiBr as the eluent, and polymethyl methacrylate standards (molar mass range 800 - 2200000 g / mol) by a method similar to that described by S. Chen et al., Polym. Chem., 2014, 5(18), 5310.

[0048] For lower molecular weights, the number-average molecular weight can also be determined by 1 H NMR-spectroscopy.

[0049] As described by M-H. Alvès et al., ibid., the degree of substitution is determined by 1 H NMR spectroscopy from the amount of anomeric hydroxyl groups to methyl groups in the terpene. The degree of substitution refers to the average number of hydrophobic compounds selected from terpenes, polyterpenes, and polyterpene ethers relative to the average number of sugar repeating units of the polysaccharide compound.

[0050] The conjugates used according to the invention comprise a sugar compound selected from disaccharides, oligosaccharides, and polysaccharides. Preferably, the molecule of the conjugate comprises a single sugar compound per molecule.

[0051] For the purposes of the present invention, the term "disaccharide" should be understood as a sugar compound in which the molecule has two identical or different monosaccharide units, which are linked by a glycosidic bond to form a disaccharide molecule.

[0052] For the purposes of the present invention, the terms "oligosaccharide" and "polysaccharide" refer to sugar compounds having a number average of at least 3, such as from 3 to 1000, especially from 3 to 500, identical or different monosaccharide units, which are linked by glycosidic bonds to form linear or branched oligosaccharide or polysaccharide molecules. In this regard, the boundary between oligosaccharides and polysaccharides is not clearly defined. Typically, the term "oligosaccharide" refers to a sugar compound in which the molecule has an average of 3 to 10 identical or different monosaccharide units, which are linked by glycosidic bonds to form linear or branched oligosaccharide molecules. Typically, the term "polysaccharide" should be understood to mean a sugar compound in which the molecule has an average of more than 10, such as from 10 to 1000 or from 10 to 500, identical or different monosaccharide units, which are linked by glycosidic bonds to form linear or branched polysaccharide molecules.

[0053] Preferably, the sugar compound of the conjugate has a number average of from 2 to 1000, especially from 5 to 1000, in particular from 10 to 500, monosaccharide repeating units. The number average of the monosaccharide repeating units relates to the molecular weight of the sugar compound and, therefore, it can be determined by size exclusion chromatography using a multi-angle light scattering detector, as described, for example, by S. et al. in "Characterisation of molecular parameters of dietary fibre components from pea and lupins with regard to their physico-chemical properties", PhD thesis, pp. 31 - 36, TU Berlin 2004. Alternatively, the number average molecular weight can be determined by osmometry, as described by Y. Rong, M. Sillick and C M. Gregson in Journal of Food Science 2009, 74(1), pp. C33 - 040 ("Determination of Dextrose Equivalent Value And Number Average Molecular Weight Of Maltodextrin By Osmometry").

[0054] Suitable polysaccharides have a number average molecular weight (Mn) in the range from 1000 to 100,000 Daltons, particularly in the range from 1200 to 70,000 Daltons and especially in the range from 1300 to 50,000 Daltons and a weight average molecular weight (M W ) in the range from 1100 to 1,500,000 Daltons, particularly in the range from 1500 to 1,000,000 Daltons and especially in the range from 2000 to 500,000 Daltons. The dispersity (i.e., the ratio of M W / M N ) is typically in the range from 1.5 to 20, particularly in the range from 1.5 to 12. The molecular weights given herein refer to the values determined by size exclusion chromatography as described above.

[0055] Typically, suitable polysaccharides are characterized in that a 2% by weight solution of their sodium salts in deionized water has a Brookfield viscosity in the range from 2 to 20,000 mPas, particularly in the range from 5 to 10,000 mPas and especially in the range from 10 to 5000 mPas. The viscosity values herein refer to the values determined by a Brookfield rotational viscometer according to DIN ISO 2555:2018-09 using spindle RV5 at 25 °C and a rotational speed of 20 revolutions per minute.

[0056] In the case of oligosaccharides and polysaccharides, the sugar molecules can be linear or branched.

[0057] The sugar compound can be composed of identical sugar repeating units or different sugar repeating units. The sugar repeating units forming the sugar compound are typically selected from nonionic hexoses and nonionic deoxyhexoses, such as glucose, mannose, rhamnose, arabinose and galactose and combinations thereof. However, the sugar repeating units can contain anionic monosaccharide units (such as galacturonic acid) and / or basic monosaccharide units (such as glucosamine units or N-acetylglucosamine units).

[0058] The sugar compound is typically a nonionic sugar compound selected from nonionic disaccharides, nonionic oligosaccharides and nonionic polysaccharides. In particular, the sugar compound is a nonionic disaccharide, oligosaccharide or polysaccharide compound formed from aldohexoses, particularly glucose. In particular, the sugar compound is selected from nonionic oligosaccharides or polysaccharides, particularly nonionic oligosaccharides or polysaccharides formed from aldohexoses, particularly glucose.

[0059] Suitable oligosaccharides are in particular starch degradation products having an average number of glucose units in the range from 3 to 10, which corresponds to a DE (dextrin equivalent) value in the range from 10 to 40. DE is a measure of the amount of reducing sugar present in the sugar product, expressed as a percentage of the dry basis relative to dextrose. Usually, DE is determined according to the method of Lane and Eynon and expressed as invert sugar %, or determined according to the method of Luff - Schoorl and expressed in meq glucose / g. The corresponding methods are described in the Official Journal of the European Communities [Official Journal of the European Communities], No. L / 239 / 24 - 52 (79 / 786 / EEC) of 22 September 1979, methods 6 (Luff - Schoorl) and 7 or 8 (Lane Eynon).

[0060] In a preferred group of embodiments, the sugar compound of the conjugate is such an oligosaccharide or polysaccharide compound having on average (number - average) 5 to 1000 or 10 to 500 identical or different monosaccharide units, which are linked by glycosidic bonds to form a linear or branched polysaccharide molecule. The polysaccharide is in particular a glucan, i.e., a polysaccharide made of glucose units. In particular, the glucan is an α - glucan, which is in particular selected from the group consisting of: dextran, pullulan, and starch degradation products (degraded starch) (such as dextrin). Thus, the polysaccharide of the conjugate is a glucan, which is in particular selected from dextran, pullulan, dextrin, and combinations thereof. In a preferred group of embodiments, the polysaccharide of the conjugate is dextran, i.e., an α - 1,6 - glucan having α - 1,3 - branches.

[0061] The conjugate of the present invention comprises at least one hydrophobic compound. According to the present invention, the hydrophobic compound is selected from terpenes, polyterpenes, and polyterpene ethers. The hydrophobic compound can be attached directly to an atom (e.g., carbon or oxygen of the sugar compound) of the sugar compound by a covalent bond or through a divalent linking group, or exists as a group R (which is derived from a terpene compound, polyterpene, or polyterpene ether compound).

[0062] Thus, the conjugate molecule comprises at least one group R, which is a group of a terpene molecule, polyterpene molecule, or polyterpene ether molecule.

[0063] The term "terpenyl" refers to a group derived from terpenes, terpene alcohols, and oxidized terpene alcohols, in particular derived from acyclic, monocyclic, or bicyclic monoterpenes or sesquiterpenes or derived from monoterpenol or sesquiterpenol as described herein.

[0064] The term "polyterpene group" refers to a group of polyterpenes.

[0065] The term "polyterpene ether group" refers to a group of polyterpene ethers.

[0066] The term "terpenol" refers to a terpene having an alcohol OH (hydroxyl) group.

[0067] Terpenes can be hydrocarbon terpenes, terpenols, and oxidized terpenols, especially monoterpenes, sesquiterpenes, diterpenes, monoterpene alcohols (monoterpene alcohol / monoterpenol), sesquiterpene alcohols (sesquiterpene alcohol / sesquiterpenol), diterpenene alcohols (diterpene alcohol / diterpenol), oxidized monoterpenols, oxidized sesquiterpenols, or oxidized diterpenols. In this context, the terms terpene and terpene compound respectively refer to hydrocarbon terpene compounds. The term terpenol refers to a terpene compound having a hydroxyl group, especially a single hydroxyl group. The term oxidized terpenol refers to a terpenol in which the hydroxyl group has been converted to an aldehyde group, a ketone group, or a carboxyl group. Respectively, monoterpenes, monoterpenols, and oxidized monoterpenols have 10 carbon atoms, sesquiterpenes, sesquiterpenols, and oxidized sesquiterpenols have 15 carbon atoms, and diterpenes, diterpenols, and oxidized diterpenols have 20 carbon atoms. Terpenes from the following groups are preferably considered: monoterpenes, monoterpenols, oxidized monoterpenols, sesquiterpenes, sesquiterpenols, and oxidized sesquiterpenols.

[0068] Terpene compounds can be saturated or carry an olefinic double bond. They can be acyclic or alicyclic. Preferred terpene compounds are acyclic terpene compounds and alicyclic terpene compounds having a single 5- or 6-membered hydrocarbon monocyclic ring or a single 6- to 9-membered hydrocarbon bicyclic ring. Particularly preferred terpene compounds have 10 or 15 carbon atoms and are selected from acyclic terpene compounds and alicyclic terpene compounds having a single 5- or 6-membered hydrocarbon monocyclic ring or a single 6- to 9-membered hydrocarbon bicyclic ring.

[0069] Examples of acyclic terpene compounds include, but are not limited to, citronellol, geraniol, nerol, linalool, myrcenol, lavandulol, ipsdienol, farnesol, and nerolidol. Examples of cyclic terpene compounds include, but are not limited to, menthol, terpineol, terpinene, pulegol, borneol, and isoborneol.

[0070] In the specific group (0) of the embodiments, the hydrophobic compound is selected from terpene alcohol compounds, which are particularly selected from monoterpene alcohols, sesquiterpene alcohols and diterpene alcohols, oxidized monoterpene alcohols, oxidized sesquiterpene alcohols and oxidized diterpene alcohols, and polyterpene ether compounds, wherein the terpene units of the polyterpene ether compounds are derived from monoterpene alcohols, sesquiterpene alcohols and diterpene alcohols. In this specific group (0) of the embodiments, the hydrophobic compound is particularly selected from monoterpene alcohols, sesquiterpene alcohols, oxidized terpineol and oxidized sesquiterpene alcohols. In this specific group of the embodiments, the preferred terpene alcohol compounds and oxidized terpene alcohol compounds are acyclic terpene alcohol compounds, oxidized terpene alcohol compounds, alicyclic terpene alcohol compounds and oxidized alicyclic terpene alcohol compounds, wherein the alicyclic terpene alcohol compounds and alicyclic oxidized terpene alcohol compounds have a single 5- or 6-membered hydrocarbon monocyclic or a single 6- to 9-membered hydrocarbon bicyclic. The particularly preferred terpene alcohol compounds and oxidized terpene alcohol compounds of this group (0) of the embodiments have 10 or 15 carbon atoms and are selected from acyclic terpene alcohol compounds, oxidized acyclic terpene alcohol compounds, alicyclic terpene alcohol compounds and oxidized alicyclic terpene alcohol compounds, wherein the alicyclic terpene alcohol compounds and alicyclic oxidized terpene alcohol compounds have a single 5- or 6-membered hydrocarbon monocyclic or a single 6- to 9-membered hydrocarbon bicyclic. In this specific group (0) of the embodiments, the hydrophobic compound may also preferably be a polyterpene ether compound, which is derived from monoterpene alcohols and sesquiterpene alcohols, particularly derived from acyclic monoterpene alcohols and acyclic sesquiterpene alcohols.

[0071] In this group (0) of the embodiments, the terpene alcohols are particularly selected from citronellol, geraniol, nerol, linalool, myrcenol, lavandulol, ipsdienol, farnesol, nerolidol, menthol, terpineol, bulnesol, borneol and isoborneol, wherein citronellol, nerol, geraniol, myrcenol, bulnesol, menthol and their combinations are particularly preferably considered.

[0072] In this group (0) of the embodiments, the polyterpene ether compounds are particularly derived from citronellol, geraniol, nerol, linalool, myrcenol, lavandulol, ipsdienol, farnesol, nerolidol, menthol, terpineol, bulnesol, borneol and isoborneol, wherein citronellol, nerol, geraniol, myrcenol and their combinations are particularly preferably considered.

[0073] In a specific group (1) of the embodiments, the group R in formulas (I) and (II) is selected from terpene groups, in particular from the group consisting of monoterpene groups and sesquiterpene groups. In this context, it should be clearly understood that the terpinyl group R is derived from terpineol or oxidized terpineol having the formula R-OH. Thus, the term "derived from" should be clearly understood such that the moieties R and R-O in formulas (I) and (II) are respectively derived from terpineol or oxidized terpineol ROH. In this specific group (1) of the embodiments, the group R in formulas (I) and (II) is particularly derived from monoterpenols or sesquiterpenols, in particular from acyclic monoterpenols or sesquiterpenols or alicyclic monoterpenols or sesquiterpenols having a single 5- or 6-membered hydrocarbon monocyclic or a single 6- to 9-membered hydrocarbon bicyclic. In this group (1) of the embodiments, the group R is particularly derived from citronellol, geraniol, nerol, linalool, myrcenol, lavandulol, ipsdienol, farnesol, nerolidol, menthol, terpineol, bulnesol, borneol and isoborneol, among which citronellol, nerol, geraniol, myrcenol, bulnesol, menthol and their combinations are particularly preferably considered.

[0074] In a particular subgroup (1a) of group (1) of the embodiments, the group R in formulas (I) and (II) is selected from 3,7-dimethyloct-6-en-1-yl, 3,7-dimethyloctan-1-yl, 2,6-dimethyl-2,6-octadien-8-yl and 5-methyl-2-(propan-2-yl)-cyclohexan-1-yl.

[0075] In another group (2) of the embodiments, the group R in formulas (I) and (II) is a polyterpene ether group, wherein the terpene units of the polyterpene ether have 10, 15 or 20 carbon atoms, particularly 10 or 15 carbon atoms and especially 10 carbon atoms. The polyterpene ether may have a terminal hydrogen atom or an alkyl or alkenyl group (which has 8 to 20 carbon atoms). In group (2) of the embodiments, polyalkylene ether groups derived from acyclic terpenes, particularly from acyclic monoterpenes and sesquiterpenes, are preferably considered.

[0076] In particular, the terpene units in the polyterpene ether group have the formula Alk:

[0077]

[0078] wherein R 1 represents a straight-chain or branched-chain alkylene group having 6, 11 or 16 carbon atoms, particularly 6 or 11 carbon atoms, and the zigzag line indicates the point of attachment to the oxygen atom of the polyalkylene ether.

[0079] In particular, the polyterpene ether group has the formula PAE:

[0080]

[0081] wherein R1 represents a straight-chain or branched alkylene group having 6, 11 or 16 carbon atoms, especially 6 or 11 carbon atoms, n is an integer from 0 to 20, especially from 0 to 10 and particularly from 0 to 4, and the zigzag line indicates the point of attachment to the carbon atom of the linking group or sugar.

[0082] In groups (1), (1a) and (2) of the examples, the preferred options given for the sugar compounds apply in the same way. In particular, the sugar compounds are selected from disaccharides, oligosaccharides and polysaccharide compounds, where the polysaccharide is an α-glucan such as dextran, amylose, pullulan, starch and starch degradation products (such as dextrin). In groups (1), (1a) and (2) of the examples, the sugar is especially dextran.

[0083] The weight ratio of group R to the polysaccharide in the non-ionic conjugate is often in the range from 20:1 to 1:80. If the polysaccharide is used as a stabilizer for an o / w emulsion, the weight ratio of group R to the polysaccharide in the non-ionic conjugate is preferably in the range from 1:1.5 to 1:80, especially in the range from 1:2 to 1:60.

[0084] In the conjugates of the present invention, especially in groups (1) and (1a) of the examples, the sugar compound is replaced by at least one aqueous compound selected from terpenes, polyterpenes and polyterpene ethers. The sugar compound of the conjugate can carry a single hydrophobic compound or have a degree of substitution of hydrophobic compounds or group R in the range up to 300 mol-%, especially in the range from 1 to 200 mol-% and particularly in the range from 1 to 100 mol-%, respectively, relative to the monosaccharide units of the sugar compound. If the conjugate of the present invention is used in an o / w emulsion, the sugar of the conjugate preferably has a degree of substitution in the range from 1 to 100 mol-%, especially in the range from 5 to 100 mol-%, particularly in the range from 5 to 60 mol-%, relative to the monosaccharide units of the sugar.

[0085] Group R can be covalently bound directly to an atom of the sugar (e.g., an oxygen atom), or can be covalently bound to the sugar via a linking group, depending on the way the conjugate is produced. Typically, the linking group has 1 or 2 functional groups such as a carbonyl group, a carboxyl group, a urea group or a carbamate group or a secondary amino group or an imino group, where one group is derived from the reaction of the hydrophobic compound with the carbohydrate, and the optional second group can be derived from the functionalization or activation of the hydrophobic compound.

[0086] In specific groups (3) and (4) of the examples of the present invention, the terpene compound is present in the conjugate molecule in the form of a group having formula (I) (group 3) or formula (II) (group 4):

[0087] R-O-(Y) k -A1 -X 1 -(I)

[0088] wherein in formula (I), the variables R, k, Y, A 1 , X 1 are as defined herein, and wherein

[0089] R is in particular a terpenyl group;

[0090] k is 0 or 1, in particular 1;

[0091] Y is C(O) or C(O)NH, in particular C(O);

[0092] A 1 is a direct bond or an alkylene group having 1 to 6 carbon atoms (C1-C6 alkylene), and wherein A 1 is in particular a C2-C6 alkylene;

[0093] X 1 is C(O), or may also be OC(O) or NHC(O) if k = 1 and A 1 is a C2-C6 alkylene, wherein X 1 is in particular C(O), and

[0094] wherein X 1 is attached to an oxygen atom of a sugar compound, in particular an oxygen atom of a polysaccharide;

[0095] R-O-(Y) k -A 1 -X 2 -A 2 -X 3 -(II)

[0096] wherein in formula (II), the variables R, k, Y, A 1 , A 2 , X 2 and X 3 are as defined herein, and wherein

[0097] R is in particular a terpenyl group, a polyterpenyl group or a polyterpenyl ether group,

[0098] k is 0 or 1, in particular 1

[0099] Y is C(O) or C(O)NH, in particular C(O)

[0100] A 1 is a direct bond or an alkylene group having 1 to 6 carbon atoms (C1-C6 alkylene) and wherein A 1 is in particular a C2-C6 alkylene,

[0101] X2 is C(O)NH or NHC(O)NH, especially C(O)NH,

[0102] A 2 is an alkylene (C2-C 10 alkylene) having 2 to 10 carbon atoms, especially a C2-C 10 alkylene in which 1, 2 or 3 non-adjacent carbon atoms of the alkylene can be replaced by oxygen atoms,

[0103] X 3 - is N= or NH-, i.e., imino or amino nitrogen,

[0104] and in which X 3 is attached to an oxygen atom of a carbon atom of a sugar compound, especially a polysaccharide.

[0105] Particularly preferred are the conjugates of group (3) of the examples,

[0106] R-O-(Y) k -A 1 -X 1 -(I)

[0107] wherein in formula (I), the variables R, k, Y, A 1 , X 1 are as defined herein, and wherein

[0108] R is especially a terpenyl group;

[0109] k is especially 1;

[0110] Y is C(O);

[0111] A 1 is especially a C2-C6 alkylene;

[0112] X 1 is C(O).

[0113] In groups (3) and (4) of the examples, the group R is preferably according to groups (1), (1a) and (2) of the examples. In groups (3) and (4) of the examples, the preferences given for the sugar apply in the same way. In particular, polysaccharides are preferred, which are α-glucans such as dextran, amylose, pullulan, starch and starch degradation products (such as dextrin). In groups (3) and (4) of the examples, the sugar is especially dextran.

[0114] In particular, the sugar of the conjugate of groups (3) and (4) of the examples has a degree of substitution with groups of formula (I) or (II) in the range from 1 to 300 mol-%, in particular in the range from 5 to 200 mol-%, relative to the monosaccharide units of the sugar. If the conjugate of groups (3) and (4) of the examples is used in an o / w emulsion, the sugar of the conjugate preferably has a degree of substitution with groups of formula (I) or (II) in the range from 1 to 100 mol-%, in particular in the range from 5 to 100 mol-%, especially in the range from 5 to 60 mol-%, relative to the monosaccharide units of the sugar.

[0115] According to group (5) of the examples, the conjugate is a graft copolymer of a polysaccharide. In this graft copolymer, the polysaccharide forms the backbone of the hydrophobic compound, which is attached directly or via a linking group to the monosaccharide repeating units of the polysaccharide backbone, i.e., the group R is present as a group of formula (I) or (II) respectively. The graft copolymer generally has a degree of substitution with the hydrophobic compound or group (I) or (II) in the range from 1 to 300 mol-%, in particular in the range from 5 to 200 mol-%, especially in the range from 10 to 200 mol-%, relative to the monosaccharide units of the polysaccharide. If the conjugate of group (5) of the examples is used in an o / w emulsion, the sugar of the conjugate preferably has a degree of substitution in the range from 1 to 100 mol-%, in particular in the range from 5 to 100 mol-%, especially in the range from 5 to 60 mol-%, relative to the monosaccharide units of the sugar.

[0116] In group (5) of the examples, the group R is preferably according to groups (1), (1a) and (2) of the examples. In particular, the group R is a terpene group or a polyterpene ether group. In group (5) of the examples, the group R is preferably present as a group of formula (I) as defined in group (3) of the examples. The preferences given for the polysaccharide in group (5) of the examples apply in the same way. In particular, the polysaccharide is an α-glucan, such as dextran, pullulan and starch degradation products (such as dextrin). In group (5) of the examples, the polysaccharide is especially dextran.

[0117] According to another group (6) of the examples, the conjugate is a block copolymer. Such a block copolymer comprises a polysaccharide block and at least one block formed from one or more hydrophobic compounds, which are attached to at least one of the terminal sugar units of the polysaccharide block. If the polysaccharide is linear, 1 or 2 hydrophobic compounds are attached to its ends.

[0118] In the group (6) of the embodiments, the group R is preferably according to the groups (1), (1a) and (2) of the embodiments. In particular, the group R is a polyterpenyl ether group. In the group 5 of the embodiments, the group R preferably exists as a group having the formula (II) as defined in the group (4) of the embodiments. In the group (6) of the embodiments, the preferences given for the polysaccharides apply in the same way. In particular, the polysaccharide is an α-glucan, such as dextran, pullulan, starch and starch degradation products (such as dextrin). In the group (6) of the embodiments, the polysaccharide is especially dextran.

[0119] The weight ratio of the hydrophobic compound to the sugar compound in the conjugate is in the range of 3:1 to 1:80, especially in the range of 2:1 to 1:60.

[0120] In a particularly preferred group (7) of the embodiments, the hydrophobic compound in the conjugate is directly bound to the oxygen atom of the sugar or exists as a group having the formula (I). If the hydrophobic compound in the conjugate is directly bound to the oxygen atom of the sugar compound, the hydrophobic compound is preferably an oxidized terpenol which bears a carboxyl group that forms an ester group with the oxygen atom of the sugar compound.

[0121] In another particularly preferred group (8) of the embodiments, the hydrophobic compound exists as a group having the formula (II). In this group, R in the formula (II) is especially a polyterpene ether group.

[0122] The conjugate of the present invention can be prepared by a method similar to the known methods for producing conjugates of sugars and hydrophobic organic compounds, such as those described, for example, in the following documents: CN 112390834; JP-H 03292301; JP61069801 A; L. Billon et al. Biomacromolecules (2014), 15(1), 242-251; S. Otto et al. Carbohydrate Polymers 254(2021)117280; A. Durand et al. Langmuir (2004), 20, 6956-6963; Save et al. Biomacromolecules (2022), 23, 2536-2551.

[0123] For example, a compound having the formula (III)

[0124] R-L (III),

[0125] wherein R is as defined herein and L is a leaving group (such as bromine, iodine, C1-C4-alkyl sulfonate or tosylate), typically reacting with the sugar in the presence of a base catalyst, whereby the group R is covalently bound to the oxygen atom of the sugar.

[0126] It is also possible to start from a compound of formula (IV)

[0127] R-OH (IV)

[0128] wherein R is as defined herein. In the compound (IV), the OH group is activated to form a leaving group or to couple with a compound having additional functionality that is capable of forming a covalent bond with one of the OH groups of the sugar or with another reactive group previously introduced into the sugar.

[0129] For example, a compound of formula (IV) can be converted into a reactive ester capable of reacting with the OH group of the sugar, such as a chloroformate or carbonate of formula (IVa) or (IVb).

[0130] R-O-C(O)-Cl (IVa)

[0131] R-O-C(O)-OR’ (IVb)

[0132] In the compounds of formula (IVa) and (IVb), the group R is as defined herein, and the group R’ in formula (IVb) is C1-C4-alkyl (such as methyl or ethyl) or hydrogen.

[0133] In a particularly preferred group of embodiments, the compound (IV) is converted into a compound of formula (V),

[0134] R-O-(Y) k -A-Z (V)

[0135] wherein

[0136] R is as defined herein,

[0137] k is 0 or 1, especially 1

[0138] Y is C(O) or C(O)NH, especially C(O)

[0139] A is a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, especially an alkylene group,

[0140] Z is an isocyanate group, a COOH group or an activated carboxyl group, such as a reactive ester group (e.g., the group COOR’) or an acid anhydride group.

[0141] For example, a compound having the formula (IV) can be reacted with an aliphatic dicarboxylic acid having 2 to 8 carbon atoms or its di-C1-C4-alkyl ester under esterification conditions to obtain a compound having the formula (V), where k = 1, Y = C(O) and Z = COOH or C(O)-O-C1-C4-alkyl. Suitable dicarboxylic acids include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, and pimelic acid.

[0142] Alternatively, a compound having the formula (IV) can be reacted with an aliphatic diisocyanate having 3 to 8 carbon atoms under urethane-forming reaction conditions (such as the conditions described in JP-H 03292301) to obtain a compound having the formula (V), where A is an alkylene group having 1 to 6 carbon atoms, k = 1, Y = C(O)NH and Z = N=C=O. Suitable diisocyanates include, for example, methane diisocyanate, ethane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, and hexane diisocyanate.

[0143] A compound having the formula (IV) can be reacted with a compound having the formula (VI)

[0144] L-A-C(O)-OR”(VI)

[0145] where L is a leaving group (such as Br or I), A is an alkylene group having 1 to 6 carbon atoms, and R” is H or C1-C4 alkyl.

[0146] Obviously, the compounds having the formulae (IVa), (IVb) and (V) thus obtained carry functional groups reactive towards the OH groups of the sugar and can therefore be coupled to the sugar under suitable reaction conditions described in the prior art or in the examples of the present application. Thereby, conjugates of the sugar and the compounds having the formulae (IVa), (IVb) and (V) are obtained. In a preferred group of embodiments, these conjugates are in the form of graft polymers, where some of the OH groups of the polysaccharide compound are replaced by groups bearing the group R (such as a group having the formula (I)).

[0147] The sugar can also be activated by introducing one or more reactive groups capable of reacting with a suitable compound bearing the group R. For example, the sugar can be reacted with a diamino compound having two primary amino groups, in particular a C2-C 10 alkylenediamine having the formula H2N-A’-NH2, where A’ is a C2-C 10 alkylen, where C2-C 10One, two or three non-adjacent carbon atoms of the alkylene group can be replaced by oxygen atoms. Thus, the aldehyde carbon atom of the terminal sugar moiety is converted to an imine, which is then hydrogenated to obtain a sugar bearing an aminoalkylamino group at the terminal sugar moiety. The primary amino group of the aminoalkylamine group can be reacted with a compound of formula (IVa), (IVb) or (V), thereby obtaining a conjugate in which the terminal sugar unit bears a group R in the form of a group of formula (II).

[0148] Conjugates of the preferred group (3) of the examples (wherein X 1 is C(O)) are prepared in particular by reacting a sugar compound with a compound of formula (V) (wherein Z is COOH) in the presence of an enzyme capable of catalyzing an esterification reaction, such as a lipase, in particular an immobilized lipase. Similarly, conjugates can be prepared in which an oxidized terpenol compound bearing a carboxyl group is directly attached to the sugar compound. Conjugates of the preferred group (4) of the examples (wherein X 2 is C(O)NH) can be prepared by reacting a sugar compound bearing at least one group NH2-A 2 -X 3 - with a compound of formula (V) (wherein Z is COOH) in the presence of an enzyme capable of catalyzing an amidation reaction, such as a lipase, in particular an immobilized lipase. Similarly, conjugates can be prepared in which an oxidized terpenol compound bearing a carboxyl group is directly attached to the sugar compound. These methods have not been described in the art and are therefore part of the present invention.

[0149] Accordingly, the present invention also relates to a method comprising reacting a sugar compound or a sugar compound bearing at least one group NH2-A 2 -X 3 - with a compound of formula (V) (wherein Z is COOH) or with an oxidized terpenol bearing a carboxyl group in the presence of an enzyme capable of catalyzing an esterification or amidation reaction, such as a lipase, in particular an immobilized lipase.

[0150] Preferably, the sugar compound used in the method of the present invention is a polysaccharide compound, which optionally bears at least one group NH2-A 2 -X 3 -. In particular, the polysaccharide compound is selected from α-glucans such as dextran, pullulan, starch and starch degradation products such as dextrin. In particular, the polysaccharide compound is dextran, which optionally bears at least one group NH2-A 2 -X 3 -.

[0151] Suitable enzymes capable of catalyzing an esterification or amidation reaction, such as lipases, are commercially available, for example, from Novozyme.

[0152] The reaction is preferably carried out in an aprotic organic solvent such as dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, acetonitrile, tetrahydrofuran, dimethylpropyleneurea, acetone, butanone, sulfolane, pyridine, triethylamine, hexamethylphosphoramide or a mixture thereof.

[0153] Preferably, the water formed in the esterification reaction or transesterification reaction is removed, for example, by distillation and / or by using molecular sieves.

[0154] As previously mentioned, the conjugates of the present invention, preferably the nonionic conjugates of the present invention, stabilize aqueous emulsions of water-immiscible liquids. To this end, a stabilizing amount of the conjugate is incorporated into the emulsion of the water-immiscible liquid.

[0155] Preferably, the aqueous emulsion of the water-immiscible liquid is an oil-in-water emulsion (o / w emulsion). An oil-in-water emulsion is defined as a mixture containing two immiscible liquids (i.e., oil and water), where the oil is dispersed into the water. Thus, the oil constitutes the dispersed phase of the o / w emulsion, while the water constitutes the continuous phase. In a water-in-oil emulsion (w / o emulsion), the water constitutes the dispersed phase in the continuous oil phase.

[0156] Depending on the energy input into the mixture of the aqueous phase and the water-immiscible liquid, the droplet size can be controlled. In addition, the type and amount of the dispersant described above affect the size of the emulsion droplets in equilibrium. Suitable amounts can be selected by conventional methods. For the purposes of the present invention, it has been found that it is beneficial if the final average particle size D[v,0.5] of the microparticles will not exceed 400 μm, especially 200 μm and particularly 100 μm.

[0157] Herein and hereinafter, all numbers for particle size, particle diameter and particle size distribution, including the D[v,0.1], D[v,0.5], D[v,0.9], D[4,3] and D[3,2] values, are based on the particle size distribution determined by static laser scattering of a sample of the microparticles according to ISO 13320:2009. The abbreviation SLS is also used hereinafter to denote "static laser scattering according to ISO 13320:2009". In view of this, the D[v,0.1] value means that 10% by volume of the particles of the measured sample have a particle diameter lower than the value reported as D[v,01]. Thus, the D[v,0.5] value means that 50% by volume of the particles of the measured sample have a particle diameter lower than the value reported as D[v,0.5], and the D[v,0.9] value means that 90% by volume of the particles of the measured sample have a particle diameter lower than the value reported as D[v,0.9]. The D[4,3] value is the volume-weighted average determined by means of SLS, which is also known as the De Brouckere average and corresponds to the mass average of the particles of the present invention. The D[3,2] value is the surface-weighted average determined by means of SLS, which is also known as the Sauter mean diameter (SMD).

[0158] Although stirring will generally produce droplets having an average droplet size D[v,0.5] of at most or below 400 μm, in particular at most 200 μm and especially at most 100 μm, for example in the range from 0.5 to 400 μm, in particular 1 to 200 μm, especially 1 to 100 μm, this is achieved by means of a device for generating a high shear field. Sufficient shear energy can also be introduced by vigorous stirring such that an average droplet size with a D[v,0.5] value in the range from 0.5 to 400 μm, preferably 1 to 200 μm and especially 1 to 100 μm is obtained. If a higher shear energy input is desired, it may be advantageous to use a device for generating a high shear field.

[0159] By adjusting the droplet size and the droplet size distribution of the emulsion, in particular of the o / w emulsion, the particle size and the particle size distribution of the final droplets containing the organic active compound can be adjusted. In other words, a small average particle size of the droplets is achieved by providing an emulsion, in particular an o / w emulsion, with a small average droplet size, and likewise, a narrow droplet size distribution of the emulsion, in particular of the o / w emulsion, will result in a narrow particle size distribution of the droplets containing the organic active compound obtained.

[0160] Suitable stirrer types include propeller stirrers, impeller stirrers, disk stirrers, paddle stirrers, anchor stirrers, pitched blade stirrers, crossbeam stirrers, helical stirrers, screw stirrers, etc.

[0161] A suitable device for shearing, i.e., for generating a high-shear field, is a disperser operating on the rotor-stator principle, i.e., a rotor-stator mixer, such as a toothed-ring disperser, also known as a gear disperser, as well as other colloid mills and disk mills, high-pressure homogenizers, also known as high-pressure mixers and ultrasonic homogenizers. High shear can also be achieved by using a dispersing disk or a cross-blade stirrer with one or more stages. Among the devices for shearing, preference is given to dispersers operating on the rotor-stator principle for generating a shear field, in particular toothed-ring dispersers. Depending on the machine size and dispersing performance, the diameters of the rotor and stator typically range between 1 cm and 40 cm. Depending on the construction type, the rotational speed of such dispersers usually ranges from 500 to 20,000 rpm, especially from 1000 to 15,000 rpm (revolutions per minute). Of course, machines with a large rotor diameter rotate at the lower end of the speed range, while machines with a small rotor diameter typically operate at the upper end of the speed range. The circumferential speed of the rotor typically ranges between 5 and 50 m / s. The distance between the rotating part and the stationary part of the dispersing tool is usually 0.1 to 3 mm.

[0162] As mentioned above, the droplet size can be controlled by the input of shear energy into a mixture of an aqueous phase and a water-immiscible liquid. Taking into account heat losses, the shear energy introduced can be directly derived from the power consumption of the device for generating the shear field. Thus, the input of shear energy into the o / w emulsion is preferably 250 to 25,000 watt h / m 3 Batch size. Based on the motor current calculation, particular preference is given to considering an energy input of 500 to 15,000, especially 800 to 10,000 watt h / m 3 Batch size.

[0163] In a preferred embodiment, emulsification is carried out such that the emulsion droplets of the emulsion, especially the o / w emulsion, have an average diameter D[v,0.5] of at most or less than 400 μm, determined by light scattering, for example in the range from 0.5 to 400 μm, especially in the range from 1 to 200 μm and particularly in the range from 1 to 100 μm. For this purpose, emulsification typically comprises mixing the solution of step i. with the aqueous phase and homogenizing the mixture. Homogenization is typically achieved by subjecting the mixture to high shear using a suitable device as described above. Mixing and homogenization can be carried out sequentially or simultaneously.

[0164] Frequently, based on the weight of the water-immiscible liquid phase of the aqueous emulsion, especially the oil phase of the o / w emulsion containing a biocide compound, the conjugate will be used in an amount in the range from 1% to 50% by weight, especially in the range from 2% to 40% by weight, more particularly in the range from 5% to 35% by weight and especially in the range from 8% to 30% by weight.

[0165] The weight ratio of the conjugate to the water-immiscible liquid of the emulsion ranges from 1:100 to 1:1, particularly from 1:50 to 1:2, especially from 1:30 to 1:3.

[0166] For example, an aqueous emulsion of a water-immiscible liquid can be stabilized by dissolving the conjugate, particularly a non-ionic conjugate, in water used to emulsify the water-immiscible liquid. In the case where the organic active compound is solid at 22 °C, the solid is dissolved in a water-immiscible organic solvent, and preferably its solution is used to form the aqueous emulsion according to the invention. It is also possible to first mix the solid or its solution with the conjugate in a water-immiscible organic solvent, and then emulsify the mixture in water.

[0167] In the presence of a conjugate, particularly a non-ionic conjugate, the emulsification of a water-immiscible liquid in water can be achieved by mixing the components forming the emulsion, i.e., the water-immiscible liquid, water, then the conjugate, particularly a non-ionic conjugate, and optionally a water-immiscible organic solvent, in any order in a suitable mixing device. It may be beneficial for the emulsification to include a homogenization step to reduce the droplet size of the non-aqueous droplets of the emulsion. Homogenization can be achieved in a known manner, for example by using a microfluidizer or a high-pressure homogenizer.

[0168] Based on the total weight of the emulsion, the concentration of the water-immiscible liquid in the aqueous emulsion can vary and typically ranges from 0.1% to 60% by weight, particularly from 1% to 45% by weight, especially from 1.5% to 40% by weight.

[0169] The conjugate can be mainly used to stabilize any aqueous emulsion of any water-immiscible liquid. For this purpose, in principle, any water-immiscible liquid capable of being emulsified in water can be used. For example, if the water-immiscible liquid is liquid at 22 °C, it can be emulsified as such without the need for a water-immiscible solvent. If the water-immiscible liquid is solid at 22 °C, the solid compound is preferably dissolved in a water-immiscible solvent and the solution is emulsified in water.

[0170] Thus, suitable water-immiscible liquids are liquid at 22 °C or, in the case where they are solid at 22 °C, they can be dissolved in a water-immiscible solvent. Generally, the water-immiscible liquid is a non-ionic organic compound. In particular, the water-immiscible liquid is a non-ionic organic compound whose molecule has 6 to 50 non-hydrogen atoms particularly selected from C, O, S, N, P, and halogen. The miscibility of the water-immiscible liquid in water will generally not exceed 5 g / l or will be at most 3 g / l or at most 2 g / l, as determined at 20 °C and 1 mbar.

[0171] In particular, the water-immiscible liquid of the aqueous emulsion comprises at least one organic active compound, in particular at least one pesticidal compound. In this case, it is immaterial whether the organic active compound itself is liquid at 22 °C and forms non-aqueous droplets in the aqueous emulsion or is solid at 22 °C and is dissolved in a water-immiscible solvent forming the droplets in the emulsion.

[0172] Typically, the organic active compound is a non-ionic organic compound. In particular, the organic active compound is a non-ionic organic compound the molecules of which have from 6 to 50 non-hydrogen atoms selected in particular from C, O, S, N, P and the halogens. The solubility of the organic active compound in water will generally not exceed 5 g / l or will be at most 3 g / l or at most 2 g / l, as determined at 20 °C and 1 mbar.

[0173] Preferably, the organic active compound is a water-immiscible liquid at 22 °C and / or is dissolved in a water-immiscible organic solvent.

[0174] The concentration of the organic active compound in the composition can vary and typically ranges from 10 to 800 g / kg of the composition.

[0175] The organic active compound is often selected from agrochemicals, in particular pesticidal agents, aroma chemicals, pharmaceutically active compounds, vitamins, cosmetic active substances and organic effect compounds. Preference is given to agrochemicals, in particular pesticidal agents.

[0176] In a preferred group of embodiments, the organic active substance is an aroma chemical, in particular an aroma chemical that is liquid at 22 °C and 1 bar, or a mixture of two or more aroma chemicals that are liquid at 22 °C and 1 bar. Preferred aroma chemicals are hydrophobic and in particular have a solubility in deionized water of not more than 1 g / L at 25 °C.

[0177] The term "aroma chemical" is understood by the person skilled in the art to mean an organic compound that can be used as an "odorant" and / or a "flavorant". In the context of the present invention, an "odorant" is understood to mean a natural or synthetic substance having an inherent odor. In the context of the present invention, a "flavorant" is understood to mean a natural or synthetic substance having an inherent flavor. In the context of the present invention, an "odor" or "olfactory perception" is an interpretation of a sensory stimulus sent from chemoreceptors in the nose or other olfactory organs to the brain of a living being. An odor can be the result of the perception of an odorant by the nose during inhalation. In this case, air acts as an odor carrier.

[0178] Preferred aroma chemicals are selected from, for example, the following compounds:

[0179] α-Hexylcinnamaldehyde, ethyl 2-phenoxyisobutyrate (Phenirat 1 ), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably having a cis-isomer content of more than 60% by weight) (Hedione 9 , Hedione HC 9 ), 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopentadieno[g]benzopyran (Galaxolide 3 ), tetrahydrolinalool (3,7-dimethyloctan-3-ol), ethyl linalool, benzyl salicylate, 2-methyl-3-(4-tert-butylphenyl)propanal (Lilial 2 ), cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5-indanyl acetate and / or 4,7-methano-3a,4,5,6,7,7a-hexahydro-6-indanyl acetate (Herbaflorat 1 ), citronellol, citronellyl acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styryl acetate (ethyl 1-phenylacetate), octahydro-2,3,8,8-tetramethyl-2-naphthalenone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (Iso ESuper 3 ), hexyl salicylate, 4-tert-butylcyclohexyl acetate (Oryclone 1 ), 2-tert-butylcyclohexyl acetate (Agrumex HC 1 ), α-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one), n-α-methylionone, α-isomethylionone, coumarin, terpinyl acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde (Lyral 3 ), α-amylcinnamaldehyde, ethylene brassylate, (E)- and / or (Z)-3-methylcyclopentadecen-5-one (Muscenone 9 ), 15-pentadecen-11-olide and / or 15-pentadecen-12-olide (Globalide 1 ), 15-cyclopentadecanolide (Macrolide 1 ), 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl)ethanone (Tonalide 10 ), 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol 9)、2-Ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (Sandolene 1 )、cis-3-Hexenyl acetate, trans-3-Hexenyl acetate, trans-2-cis-6-Nonadienol, 2,4-Dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral 1 )、2,4,4,7-Tetramethyloct-6-en-3-one (Claritone 1 )、2,6-Dimethyl-5-hepten-1-al (Melonal 2 )、Borneol, 3-(3-Isopropylphenyl)butyraldehyde (Florhydral 2 )、2-Methyl-3-(3,4-methylenedioxyphenyl)propanal (Helional 3 )、3-(4-Ethylphenyl)-2,2-dimethylpropanal (Florazon 1 )、Tetrahydro-2-isobutyl-4-methyl-2H-pyran (Dihydrorosenon 4 )、1,4-Bis(ethoxymethyl)cyclohexane (Vertofruct 4 )、L-Isopulegol (1R,2S,5R)-2-Isopropenyl-5-methylcyclohexanol, pyranyl acetate (2-Isobutyl-4-methyltetrahydropyran-4-yl acetate), Nerol ((Z)-2,6-Dimethyl-2,6-octadien-1-ol), Nerol acetate, 7-Methyl-2H-1,5-benzodioxepin -3(4H)-one (Calone 19515 )、Cyclohexyl 3,3,5-trimethylacetate (preferably having a cis-isomer content of 70% by weight) or more and 2,5,5-Trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol S 1 )、Tetrahydro-4-methyl-2-(2-methylallyl)-2H-pyran (rose oxide), 4-Methyl-2-(2-methylpropyl)oxane or 4-Methyl-2-(2-methylpropyl)-2H-pyran (Dihydrorosan 4 )、Pentenyl acetate (=3-Methylbut-2-enyl acetate), Isoamyl acetate, Dihydromyrcenol (2,6-Dimethyloct-7-en-2-ol) and Methylheptenone (6-Methylhept-5-en-2-one) and mixtures thereof, and also mixtures thereof with one or more other fragrances.

[0180] In the context of the present invention, it is therefore preferred to combine the above fragrances or odorants with the mixtures of the present invention.

[0181] If a trade name is specified above, these refer to the following sources:

[0182] 1 Trade names of Symrise GmbH, Germany;

[0183] 2 Trade names of Givaudan AG, Switzerland;

[0184] 3 Trade names of International Flavors & Fragrances Inc., USA;

[0185] 4 Trade names of BASF SE;

[0186] 5 Trade names of Danisco Seillans S.A., France;

[0187] 9 Trade names of Firmenich S.A., Switzerland;

[0188] 10 Trade names of PFW Aroma Chemicals B.V., Netherlands.

[0189] More particularly, the advantages of the present invention are manifested in the case of aroma chemicals selected from volatile perfumes and perfume mixtures comprising at least one volatile perfume. Volatile perfumes are understood to mean perfumes having a high vapor pressure at room temperature. A perfume is considered a volatile perfume especially when it has the following property: if a droplet of the volatile perfume is applied to a strip of paper and allowed to evaporate under ambient conditions at room temperature (22 °C), its odor is no longer perceptible to an experienced perfumer 2 hours after application. Volatile perfumes particularly include the following compounds: rose oxide (tetrahydro-4-methyl-2-(2-methylpropenyl)-2H-pyran), 4-methyl-2-(2-methylpropyl)oxane or 4-methyl-2-(2-methylpropyl)-2H-pyran Pentenyl acetate (=3-methylbut-2-enyl acetate), isopentyl acetate, dihydrolinalool (2,6-dimethyl-7-octen-2-ol) and methylheptenone (6-methylhept-5-en-2-one). If an aromatic mixture containing at least one volatile perfume is used for loading, the proportion of the volatile perfume is generally at least 1% by weight, in particular at least 5% by weight, based on the total weight of the aromatic chemical mixture used for loading, for example from 1% to 99% by weight, in particular from 5% to 95% by weight.

[0190] The odorants mentioned can be combined therewith to obtain further odorants for odorant compositions or the aroma chemicals can be found, for example, in S. Arctander, Perfume and Flavor Chemicals, Volumes I and II, Montclair, N.J., 1969, the author's edition or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th Edition, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2001. Specifically, the following may be mentioned:

[0191] Extracts from natural raw materials, such as essential oils, condensed resins, absolutes, resins, balms, tinctures, for example amber tincture; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; moss absolute; laurel oil; artemisia oil; benzoin resin; bergamot oil; beeswax absolute; birch tar; bitter almond oil; savory oil; buchu leaf oil; kalua oil; juniper oil; calamus oil; camphor oil; cananga oil; cardamom oil; quinoa oil; cinnamon oil; Acacia absolute; castoreum absolute; cedar leaf oil; cedarwood oil; labdanum oil; citronella oil; lemon oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill oil; dill seed oil; eau de toilette absolute; oakmoss absolute; elemi oil; tarragon oil; lemon eucalyptus oil; eucalyptus oil; anise oil; spruce needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; guarana balsam; guarana balsam oil; helichrysum absolute Oil; Helichrysum Oil; Ginger Oil; Orris Root Absolute; Orris Root Oil; Jasmine Absolute; Calamus Oil; Blue Camellia Oil; Roman Camellia Oil; Carrot Seed Oil; Carrot Oil; Pine Needle Oil; Spearmint Oil; Kumei Oil; Lavender Oil; Lavender Absolute; Lavender Resin; Lavender Absolute; Lavender Oil; Lavender Absolute; Lavender Oil; Lemongrass Oil; Lovage Oil; Lime Oil Distilled; Lime Oil Pressed; Linalool Oil; Litsea Cubeba Oil; Bay Leaf Oil; Myristica Fragrance Oil; Mayonnaise Oil orchid oil; orange oil; cinnamon bark oil; mimosa absolute; musk seed oil; musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove flower oil; neroli oil; frankincense absolute; frankincense oil; red myrrh oil; neroli absolute; orange oil; oregano oil; palmarosa oil; patchouli oil; perilla oil; Peru balsam oil; parsley leaf oil; parsley seed oil; orange leaf oil; mint oil; pepper oil; allspice oil; pine oil; poley oil oil); rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; lavender oil; anise oil; styrax oil; marigold oil; fir oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka bean absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; brewer's yeast oil; wormwood oil; wintergreen oil; ylang-ylang oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil; and fractions thereof or components isolated therefrom.

[0192] Individual odorants are for example those from the group of

[0193] - hydrocarbons, for example 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; citronellene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;

[0194] - Aliphatic alcohols, such as hexanol; octanol; 3 - octanol; 2,6 - dimethylheptanol; 2 - methyl - 2 - heptanol; 2 - methyl - 2 - octanol; (E)-2 - hexenol; (E)- and (Z)-3 - hexenol; 1 - octen - 3 - ol; a mixture of 3,4,5,6,6 - pentamethyl - 3 / 4 - hepten - 2 - ol and 3,5,6,6 - tetramethyl - 4 - methylenehept - 2 - ol; (E,Z)-2,6 - nonadienol; 3,7 - dimethyl - 7 - methoxyoct - 2 - ol; 9 - decenol; 10 - undecenol; 4 - methyl - 3 - decen - 5 - ol;

[0195] - Aliphatic aldehydes and their acetals, such as hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2 - methyloctanal; 2 - methylnonanal; (E)-2 - hexenal; (Z)-4 - heptenal; 2,6 - dimethyl - 5 - heptenal; 10 - undecenal; (E)-4 - decenal; 2 - dodecenal; 2,6,10 - trimethyl - 9 - undecenal; 2,6,10 - trimethyl - 5,9 - undecadienal; heptanal diethyl acetal; 1,1 - dimethoxy - 2,2,5 - trimethyl - 4 - hexene; citronellyloxyacetaldehyde; (E / Z)-1-(1 - methoxypropoxy)-3 - hexene; Aliphatic ketones and their oximes, such as 2 - heptanone; 2 - octanone; 3 - octanone; 2 - nonanone; 5 - methyl - 3 - heptanone; 5 - methyl - 3 - heptanone oxime; 2,4,4,7 - tetramethyl - 6 - octen - 3 - one; 6 - methyl - 5 - hepten - 2 - one;

[0196] - Aliphatic sulfur - containing compounds, such as 3 - (methylthio)hexanol; 3 - (methylthio)hexyl acetate; 3 - mercaptohexanol; 3 - mercaptohexyl acetate; 3 - mercaptohexyl butyrate; 3 - (acetylthio)hexyl acetate; 1 - menthene - 8 - thiol;

[0197] - Aliphatic nitriles, such as 2 - nonenenitrile; 2 - undecenenitrile; 2 - tridecenenitrile; 3,12 - tridecadienenitrile; 3,7 - dimethyl - 2,6 - octadienenitrile; 3,7 - dimethyl - 6 - octenenitrile;

[0198] - Esters of aliphatic carboxylic acids, such as (E)- and (Z)-3 - hexenyl formate; ethyl acetoacetate; isopentyl acetate; hexyl acetate; 3,5,5 - trimethylhexyl acetate; 3 - methyl - 2 - butenyl acetate; (E)-2 - hexenyl acetate; (E)- and (Z)-3 - hexenyl acetate; octyl acetate; 3 - octyl acetate; 1 - octen - 3 - yl acetate; ethyl butyrate; butyl butyrate; isopentyl butyrate; hexyl butyrate; (E)- and (Z)-3 - hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2 - methylvalerate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; (E / Z)-ethyl 2,4 - decadienoate;

[0199] Methyl 2 - octynoate; Methyl 2 - nonynoate; Allyl 2 - isopentoxyacetate; Methyl 3,7 - dimethyl - 2,6 - octadienoate; 4 - Methyl - 2 - pentyl crotonate;

[0200] - Acyclic terpene alcohols, such as geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; 2,6 - dimethyl - 7 - octen - 2 - ol; 2,6 - dimethyloctan - 2 - ol; 2 - methyl - 6 - methylene - 7 - octen - 2 - ol; 2,6 - dimethyl - 5,7 - octadien - 2 - ol; 2,6 - dimethyl - 3,5 - octadien - 2 - ol; 3,7 - dimethyl - 4,6 - octadien - 3 - ol; 3,7 - dimethyl - 1,5,7 - octatriene - 3 - ol; 2,6 - dimethyl - 2,5,7 - octatriene - 1 - ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglinates and 3 - methyl - 2 - butenoates;

[0201] - Acyclic terpene aldehydes and ketones, such as geranial; neral; citronellal; 7 - hydroxy - 3,7 - dimethyloctanal; 7 - methoxy - 3,7 - dimethyloctanal; 2,6,10 - trimethyl - 9 - undecenal; geranylacetone; and also dimethyl and diethyl acetals of geranial, neral, 7 - hydroxy - 3,7 - dimethyloctanal; Cyclic terpene alcohols, such as menthol; isopulegol; α - terpineol; terpineol - 4; menthan - 8 - ol; menthan - 1 - ol; menthan - 7 - ol; borneol; isoborneol; linalool oxide; nobelol; cedrol; ambreinolide; vetiverol; guaiol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglinates and 3 - methyl - 2 - butenoates;

[0202] - Cyclic terpene aldehydes and ketones, such as menthone; isomenthone; 8 - mercaptomenthane - 3 - one; carvone; camphor; anisone; α - ionone; β - ionone; α - nor - methylionone; β - nor - methylionone; α - iso - methylionone; β - iso - methylionone; α - irone; α - damascenone; β - damascenone; β - damascenone; δ - damascenone; γ - damascenone; 1 - (2,4,4 - trimethyl - 2 - cyclohexen - 1 - yl) - 2 - buten - 1 - one; 1,3,4,6,7,8a - hexahydro - 1,1,5,5 - tetramethyl - 2H - 2,4a - methano - naphthalen - 8(5H) - one; 2 - methyl - 4 - (2,6,6 - trimethyl - 1 - cyclohexen - 1 - yl) - 2 - butenal; nootkatone; dihydronootkatone; 4,6,8 - megastigmatrien - 3 - one; α - sinensal; β - sinensal; acetylated cedarwood oil (methyl cedryl ketone);

[0203] - Cyclic alcohols, such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isobornylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0204] - Alicyclic alcohols, such as α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)pent-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pent-3-ol; 1-(2,2,6-trimethylcyclohexyl)hex-3-ol;

[0205] - Cyclic and alicyclic ethers, such as cineole; methyl cedryl ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; 1,4-bis(ethoxymethyl)cyclohexane; (ethoxymethoxy)cyclododecane; α-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;

[0206] - Cyclic ketones and macrocyclic ketones, such as 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; cis-3-methylpent-2-en-1-yl cyclopent-2-en-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-amylcyclohexanone; cyclohexadec-5-en-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indenone; 8-cyclohexadecen-1-one; 7-cyclohexadecen-1-one; (7 / 8)-cyclohexadecen-1-one; 9-cycloheptadecen-1-one; cyclopentadecanone; cyclohexadecanone;

[0207] - Alicyclic aldehydes, such as 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohex-1-en-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde;

[0208] - Alicyclic ketones, such as 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl (2,4-dimethyl-3-cyclohexen-1-yl) ketone;

[0209] - Esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-amylcyclohexyl acetate; 4-tert-amylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl isobutyrate; 4,7-methanooctahydro-5- or -6-indenyl acetate;

[0210] - Esters of alicyclic alcohols, such as 1-cyclohexylethyl crotonate;

[0211] - Esters of alicyclic carboxylic acids, such as allyl 3 - cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl cis - and trans - dihydrojasmonate; methyl cis - and trans - jasmonate; methyl 2 - hexyl - 3 - oxocyclopentanecarboxylate; ethyl 2 - ethyl - 6,6 - dimethyl - 2 - cyclohexene - 1 - carboxylate; ethyl 2,3,6,6 - tetramethyl - 2 - cyclohexene - 1 - carboxylate; ethyl 2 - methyl - 1,3 - dioxolane - 2 - acetate;

[0212] - Aryl - aliphatic alcohols, such as benzyl alcohol; 1 - phenylethanol, 2 - phenylethanol, 3 - phenylpropanol; 2 - phenylpropanol; 2 - phenoxyethanol; 2,2 - dimethyl - 3 - phenylpropanol; 2,2 - dimethyl - 3 - (3 - methylphenyl)propanol; 1,1 - dimethyl - 2 - phenylethanol; 1,1 - dimethyl - 3 - phenylpropanol; 1 - ethyl - 1 - methyl - 3 - phenylpropanol; 2 - methyl - 5 - phenylpentanol; 3 - methyl - 5 - phenylpentanol; 3 - phenyl - 2 - propen - 1 - ol; 4 - methoxybenzyl alcohol; 1 - (4 - isopropylphenyl)ethanol;

[0213] - Esters of aryl - aliphatic alcohols and aliphatic carboxylic acids, such as benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2 - phenylethyl acetate; 2 - phenylethyl propionate; 2 - phenylethyl isobutyrate; 2 - phenylethyl isovalerate; 1 - phenylethyl acetate; α - trichloromethylbenzyl acetate; α,α - dimethylphenylethyl acetate; α,α - dimethylphenylethyl butyrate; cinnamyl acetate; 2 - phenoxyethyl isobutyrate; 4 - methoxybenzyl acetate;

[0214] - Aryl - aliphatic ethers, such as 2 - phenylethyl methyl ether; 2 - phenylethyl isopentyl ether; 2 - phenylethyl 1 - ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydroatropaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6 - trimethyl - 4 - phenyl - 1,3 - dioxane; 4,4a,5,9b - tetrahydro - indeno[1,2 - d]-m - dioxin; 4,4a,5,9b - tetrahydro - 2,4 - dimethyl - indeno[1,2 - d]-m - dioxin;

[0215] - Aromatic and araliphatic aldehydes, such as benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydroatropic aldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; α-butylcinnamaldehyde; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxy-benzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal;

[0216] - Aromatic and araliphatic ketones, such as acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-naphthaleneethanone;

[0217] - Aromatic and araliphatic carboxylic acids and their esters, such as benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate; ethyl 3-methyl-3-phenylglycidate;

[0218] - Nitrogen-containing aromatic compounds, such as 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamitrile; 3-methyl-5-phenyl-2-pentenenitrile; 3-methyl-5-phenylpentanenitrile; methyl anthranilate; methyl N-methylanthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[0219] - Phenols, phenyl ethers and phenyl esters, such as estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenol acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenylacetate;

[0220] - Heterocyclic compounds, such as 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0221] - Lactones, such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 4-methyl-1,4-decanolide; 1,15-pentadecanolide; cis- and trans-11-pentadecen-1,15-olide; cis- and trans-12-pentadecen-1,15-olide; 1,16-hexadecanolide; 9-hexadecen-1,16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene 1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin.

[0222] In addition, suitable aromatic chemicals are macrocyclic carboxyaldehyde compounds as described in WO 2016 / 050836.

[0223] Particularly preferred are mixtures of L-menthol and / or DL-menthol, L-menthone, L-menthyl acetate or L-isopulegol, which are highly sought after as analogues or alternatives to what is known as dementholized oil (DMO). These mixtures of minty components are preferably used in a ratio of 20% - 40% by weight of L-menthol or DL-menthol, 20% - 40% by weight of L-menthone and 0 - 20% by weight of L-menthyl acetate, or in a ratio of 20% - 40% by weight, 20% - 40% by weight of L-menthone and 0 - 20% by weight of L-isopulegol.

[0224] The above-mentioned fragrances and fragrance mixtures can be used as such or in a solvent in which they are not a fragrance per se. Typical solvents for fragrances are in particular those having a boiling point above 150 °C under standard pressure and not dissolving the wall material, such as glycols like propylene glycol and dipropylene glycol, C8-C 22 Fatty acid C1-C 10 -alkyl esters such as isopropyl myristate, di-C6-C 10 -alkyl ethers, such as dioctyl ether (OE from BASF), di-C1-C of aliphatic, aromatic or alicyclic dicarboxylic or tricarboxylic acids, such as dialkyl phthalates like dimethyl phthalate and diethyl phthalate and mixtures thereof, dialkyl hexahydrophthalates such as dimethyl cyclohexane-1,2-dicarboxylate, diethyl cyclohexane-1,2-dicarboxylate and diisononyl 1,2-cyclohexanedicarboxylate, and dialkyl adipates, such as dibutyl adipate (e.g. from BASF 10 B), C8-C B), C8-C 22 Fatty acid triglycerides, such as vegetable oils or cosmetic oils like capryloyl / capric triglyceride (e.g. a commercial product from BASF 318), dimethyl sulfoxide and white oil.

[0225] In a further group of embodiments, the low molecular weight organic active substances are active pharmaceutical ingredients, abbreviated as API. Active pharmaceutical ingredients are typically active therapeutic ingredients, active diagnostic ingredients and active prophylactic ingredients, as well as corresponding combinations of active ingredients. The active pharmaceutical ingredients can be in an amorphous state, a crystalline state or a mixture thereof. The active pharmaceutical ingredients can be labeled with detectable labels such as fluorescent labels, radioactive labels or enzymatically or chromatographically detectable species, and used together with the label as a mixture for loading the microparticles.

[0226] At 25 °C, the API can have a water solubility of more than 10 mg / mL in deionized water. It is also possible to use an active pharmaceutical ingredient with low water solubility as the active substance, for example those having a water solubility of less than 10 mg / mL in deionized water at 25 °C. In any case, the API should have a partition coefficient of at least 1.0, especially at least 2.0, with respect to the water-immiscible liquid and the aqueous phase.

[0227] Preferred active therapeutic, diagnostic and prophylactic ingredients are those APIs suitable for parenteral administration. Representative examples of suitable APIs are the following classes and examples of APIs and alternative forms of these APIs, such as alternative salt forms, free acid forms, free base forms and hydrates:

[0228] Analgesics / antipyretics; anti-asthmatics; antibiotics; antidepressants; antidiabetics; anti-inflammatory agents / inflammation inhibitors; antihypertensives; inflammation inhibitors; anti-tumor agents; anti-anxiety agents; immunosuppressants; anti-migraine agents; sedatives / hypnotics; antianginal drugs; antipsychotics; antimanics; antiarrhythmics; anti-arthritis agents; antigout agents; anticoagulants; thrombolytics; antifibrinolytics; hemorheological agents; antiplatelet agents / platelet aggregation inhibitors; anticonvulsants; anti-Parkinson's agents; antihistamines / antipruritics; drugs for calcium regulation; antibacterial drugs; antiviral drugs; antimicrobial agent drugs; anti-infective drugs; bronchodilators; corticosteroids; steroids and hormones; hypoglycemic drugs; hypolipidemic drugs; proteins; nucleic acids; drugs that can be used to stimulate erythropoiesis; anti-ulcer drugs / anti-reflux drugs; anti-nausea drugs / antimosis drugs; fat-soluble vitamins and other drugs.

[0229] Suitable active pharmaceutical ingredients are mentioned, for example, in WO 2007 / 070852, especially on pages 15 to 19. In addition, suitable active ingredients and drugs are listed in Martindale: The Extra Pharmacopoeia, 30th edition, The Pharmaceutical Press, London 1993.

[0230] In a further group of embodiments, the organic active substance is an agrochemical compound, i.e., an organic compound for crop protection, which is also referred to as an organic crop protection agent. Agrochemicals are, for example, pesticides, especially selected from the group consisting of: fungicides, insecticides, nematicides, herbicides, pheromones and also safeners and growth regulators, which can be included as a single compound and also as a mixture of different agrochemical compounds, for example as a mixture of two or more herbicides, a mixture of two or more fungicides, a mixture of two or more insecticides, a mixture of an insecticide and a fungicide, a mixture of one or more herbicides and a safener and a mixture of one or more fungicides and a safener.

[0231] Typically, agrochemicals are liquids or solids at 20 °C and 1 bar and are generally non-volatile. At 20 °C, the vapor pressure is typically below 0.1 mbar, especially below 0.01 mbar. Agrochemicals that are particularly slightly water-soluble or even insoluble in water (especially at 25 °C) have a water solubility of no more than 5 g / L and especially no more than 2 g / L in deionized water.

[0232] Agrochemicals are known to those skilled in the art, for example from The Pesticide Manual, 17th Edition, The British Crop Protection Council, London, 2015. Suitable crop protection agents are especially listed on pages 10 to 15 of WO 2018 / 019629.

[0233] Examples of suitable insecticides are compounds from the following classes: carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosin, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides and unclassified insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, chlorbenside sulfone, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or their agriculturally acceptable salts and derivatives.

[0234] Examples of suitable fungicides are compounds from the following classes: dinitroanilines, allylamines, anilinopyrimidines, antibiotic fungicides, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic diamides, chloronitriles, cyanoacetamidoximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethyl phosphonates, ethylaminothiazole carboxamides, guanidines, hydroxy(2-amino)pyrimidines, hydroxyacetanilides, imidazoles, imidazolinones, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothioates, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinones, hydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfonamides, sulfamoyl triazoles, thiazole carboxamides, thiocarbamates, thiophanates, thiophene carboxamides, toluamides, triphenyltin compounds, triazines, triazoles and their agriculturally acceptable salts and derivatives.

[0235] Examples of suitable herbicides are compounds from the following classes: acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridinium salts, carbamates, chloroacetamides, chloro carboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenols, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorothioates, phthalimides, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, (thio)benzoic acid pyrimidylesters, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyl triazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazoloformamides, triazolo pyrimidines, triones, uracils, ureas and their agriculturally acceptable salts and derivatives.

[0236] In a specific subgroup of this group of embodiments, the crop protection agent is a crop protection agent that is liquid at 22 °C and 1 bar, or a mixture of two or more crop protection agents that are liquid at 22 °C and 1 bar. Examples of room temperature liquid active ingredients are dimethenamid, in particular its enantiomer dimethenamid-P, clomazone, metolachlor, in particular its enantiomer S-metolachlor, alachlor and cinmethylin.

[0237] In a further specific subgroup of this group of embodiments, the crop protection agent is a crop protection agent or a mixture of crop protection agents or a mixture of such active ingredients having low water solubility and a melting point not exceeding 110 °C. These include, for example, pyraclostrobin (64 °C), prochloraz (47 °C), metrafenone (100 °C), alphacypermethrin (79 °C) and pendimethalin (58 °C).

[0238] In yet another specific subgroup of this group of embodiments, the crop protection agent is a pheromone or a mixture of pheromones, optionally in combination with one or more attractants.

[0239] Pheromones are well-known chemical compounds for controlling unwanted insects. For example, Metcalf, R. L. Ullmann's Encyclopedia of Industrial Chemistry 2000, the keyword "insect control" lists suitable examples in Chapter 15.1 (Sex pheromone attractants) and Chapter 15.2 (Aggregation pheromones), and the pheromones for Lepidoptera in Table 4 of this citation are highly suitable.

[0240] Examples of pheromones include volatile alkanols and alkenols having from 5 to 18 carbon atoms, volatile alkanals and alkenals having from 5 to 18 carbon atoms, alkanones having from 6 to 18 carbon atoms, 1,7-dioxaspiro[5.5]undecane and 3- or 4-hydroxy-1,7-dioxaspiro[5.7]tridecane, benzyl alcohol, Z-(9)-tricosene, heneicosene, diacetyl, alcanoic acids having from 5 to 16 carbon atoms, such as octanoic acid, lauric acid, α-pinene, methyl eugenol, ethyl dodecanoate, tert-butyl 4-(or 5-)-chloro-2-ethylcyclohexanecarboxylate, mycrenone, cucurbitacin, Mediterranean fruit fly attractant (as commercially available) and (E,E)-8,10-dodecadien-1-ol (codlemone).

[0241] Additional examples of known pheromones are: Z-5-decenyl acetate, dodecyl acetate, Z-7-dodecenyl acetate, E-7-dodecenyl acetate, Z-8-dodecenyl acetate, E-8-dodecenyl acetate, Z-9-dodecenyl acetate, E-9-dodecenyl acetate, E-10-dodecenyl acetate, 11-dodecenyl acetate, Z-9,11-dodecadienyl acetate, E-9,11-dodecadienyl acetate, Z-11-tridecenyl acetate, E-11-tridecenyl acetate, tetradecenyl acetate, E-7-tetradecenyl acetate, Z-8-tetradecenyl acetate, E-8-tetradecenyl acetate, Z-9-tetradecenyl acetate, E-9-tetradecenyl acetate, Z-10-tetradecenyl acetate, E-10-tetradecenyl acetate, Z-11-tetradecenyl acetate, E-11-tetradecenyl acetate, Z-12-pentadecenyl acetate, E-12-pentadecenyl acetate, hexadecyl acetate, Z-7-hexadecenyl acetate, Z-11-hexadecenyl acetate, E-11-hexadecenyl acetate, octadecyl acetate, E,Z-7,9-dodecadienyl acetate, Z,E-7,9-dodecadienyl acetate, E,E-7,9-dodecadienyl acetate, Z,Z-7,9-dodecadienyl acetate, E,E-8,10-dodecadienyl acetate, E,Z-9,12-dodecadienyl acetate, E,Z-4,7-tridecadienyl acetate, 4-methoxy-cinnamaldehyde, [β]-ionone, estragol, eugenol, indole, 8-methyl-2-decyl propionate, E,E-9,11-tetradecadienyl acetate, Z,Z-9,12-tetradecadienyl acetate, Z,Z-7,11-hexadecadienyl acetate, E,Z-7,11-hexadecadienyl acetate, Z,E-7,11-hexadecadienyl acetate, E,E-7,11-hexadecadienyl acetate, Z,E-3,13-octadecadienyl acetate, E,Z-3,13-octadecadienyl acetate, E,E-3,13-octadecadienyl acetate, hexanol, heptanol, octanol, decanol, Z-6-nonenol, E-6-nonenol, dodecanol, 11-dodecenol, Z-7-dodecenol, E-7-dodecenol, Z-8-dodecenol, E-8-dodecenol, E-9-dodecenol, Z-9-dodecenol, E-9,11-dodecadienol, Z-9,11-dodecadienol, Z,E-5,7-dodecadienol, E,E-5,7-dodecadienol, E,E-8,10-dodecadienol, E,Z-8,10-dodecadienol, Z,Z-8,10-dodecadienol, Z,E-8,10-dodecadienol, E,Z-7,9-Dodecadienol, Z,Z-7,9-dodecadienol, E-5-tetradecenol, Z-8-tetradecenol, Z-9-tetradecenol, E-9-tetradecenol, Z-10-tetradecenol, Z-11-tetradecenol, E-11-tetradecenol, Z-11-hexadecenol, Z,E-9,11-tetradecadienol, Z,E-9,12-tetradecadienol, Z,Z-9,12-tetradecadienol, Z,Z-10,12-tetradecadienol, Z,Z-7,11-hexadecadienol, Z,E-7,11-hexadecadienol, (E)-14-methyl-8-hexadecen-1-ol, (Z)-14-methyl-8-hexadecen-1-ol, E,E-10,12-hexadecadienol, E,Z-10,12-hexadecadienol, dodecanal, Z-9-dodecenal, tetradecenal, Z-7-tetradecenal, Z-9-tetradecenal, Z-11-tetradecenal, E-11-tetradecenal, E-11,13-tetradecadienal, E,E-8,10-tetradecadienal, Z,E-9,11-tetradecadienal, Z,E-9,12-tetradecadienal, hexadecenal, Z-8-hexadecenal, Z-9-hexadecenal, Z-10-hexadecenal, E-10-hexadecenal, Z-11-hexadecenal, E-11-hexadecenal, Z-12-hexadecenal, Z-13-hexadecenal, (Z)-14-methyl-8-hexadecenal, (E)-14-methyl-8-hexadecenal, Z,Z-7,11-hexadecadienal, Z,E-7,11-hexadecadienal, Z,E-9,11-hexadecadienal, E,E-10,12-hexadecadienal, E,Z-10,12-hexadecadienal, Z,E-10,12-hexadecadienal, Z,Z-10,12-hexadecadienal, Z,Z-11,13-hexadecadienal, octadecenal, Z-11-octadecenal, E-13-octadecenal, Z-13-octadecenal, Z-5-decenyl-3-methylbutyrate, epoxy nonadecane (disparlure): (+)-cis-7,8-epoxy-2-methyloctadecane, seudenol: 3-methyl-2-cyclohexen-1-ol, sulcatol: 6-methyl-5-hepten-2-ol, ipsenol: 2-methyl-6-methylene-7-octen-4-ol, ipsdienol: 2-methyl-6-methylene-2,7-octadien-4-ol, attracticide mixture I: cis-2-isopropenyl-1-methylcyclobutane-ethanol, attracticide mixture II: Z-3,3-dimethyl-1-cyclohexane-ethanol, attracticide mixture III: Z-3,3-dimethyl-1-cyclohexane-acetaldehyde, attracticide mixture IV: E-3,3-Dimethyl-1-cyclohexaneacetaldehyde, cis-2-verbenol: cis-4,6,6-trimethylbicyclo[3,1,1]hept-3-en-2-ol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, [α]-pinene: 2,6,6-trimethylbicyclo[3,1,1]hept-2-ene, [α]-caryophyllene: 4,11,11-trimethyl-8-methylidene-bicyclo[7,2,0]undecane, Z-9-tricosene, ([α]-multistriatin, 2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo[3,2,1]octane, methyl eugenol: 1,2-dimethoxy-4-(2-propenyl)phenol, trimethyldioxatricyclononane (lineatin): 3,3,7-trimethyl-2,9-dioxatricyclo[3,3,1,0]nonane, chalcogran: 2-ethyl-1,6-dioxaspiro[4,4]nonane, southern pine beetle aggregation pheromone (frontalin): 1,5-dimethyl-6,8-dioxabicyclo[3,2,1]octane, endo-western pine beetle aggregation pheromone (endo-brevicomin): endo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane, exo-western pine beetle aggregation pheromone (exo-brevicomin): exo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane, (Z)-5-(1-decenyl)dihydro-2-(3H)-furanone, farnesol: 3,7,11-trimethyl-2,6,10-dodecatrien-1-ol, nerolidol 3,7-11-trimethyl-1,6,10-dodecatrien-3-ol, 3-methyl,6-(1-methylethenyl)-9-decen-1-ol acetate, (Z)-3-methyl-6-(1-methylethenyl)-3,9-decadien-1-ol acetate, (E)-3,9-methyl-6-(1-methyl-ethenyl)-5,8-decadien-1-ol acetate, 3-methylene-7-methyl-octen-1-ol propionate, (Z)-3,7-dimethyl-2,7-octadien-1-ol propionate and (Z)-3,9-dimethyl-6-(1-methyl-ethenyl)-3,9-decadien-1-ol propionate.,

[0242] Preferred pheromones are Z-9-dodecenyl acetate (as 1 is commercially available from BASF), (E7,Z9)-dodecadienyl acetate (as 2 is commercially available from BASF), (E,E)-8,10-dodecadien-1-ol (as 3 is commercially available from BASF) and Z-8-dodecenyl acetate.

[0243] Particularly preferred pheromones include (E,E)-8,10-dodecadien-1-ol, which is also known as codlemone or codlure and is commercially available (e.g., as CM-F from Suterra LLC, USA, from BASF 3). Codlemone can be used in pure form, in technical quality, or in admixture with other pheromones.

[0244] The above pheromones can be combined with one or more attractants. An attractant is a non-pesticidal material that can act in one or more of the following ways: a) to lure an insect towards the composition or a material treated with the composition; b) to lure an insect into contact with the composition or a material treated with the composition; c) to lure an insect into ingesting the composition or a material treated with the composition; and d) to lure an insect back to the composition or a material treated with the composition. Suitable attractants include non-food attractants and food attractants, also known as feeding stimulants.

[0245] Suitable non-food attractants are generally volatile materials. Volatile attractants act as baits and their type will depend on the pest to be controlled in a known manner. Non-food attractants include, for example, flavorings of natural or synthetic origin. Suitable flavorings include meat flavorings, yeast flavorings, seafood flavorings, milk flavorings, butter flavorings, cheese flavorings, onion flavorings, and fruit flavorings such as those of apple, apricot, banana, blackberry, cherry, redcurrant, gooseberry, grape, grapefruit, raspberry, and strawberry.

[0246] Suitable food attractants include:

[0247] · Proteins, including animal and plant proteins, for example in the form of meat meal, fish meal, fish extract, seafood, seafood extract, or blood meal, insect parts, cricket powder, yeast extract, egg yolk, protein hydrolysates, yeast autolysates, gluten hydrolysates, etc.;

[0248] · Carbohydrates and hydrogenated carbohydrates, especially monosaccharides and disaccharides such as glucose, arabinose, fructose, mannose, sucrose, lactose, galactose, maltose, maltotriose, maltotetraose, maltopentaose or mixtures thereof such as molasses, corn syrup, maple syrup, invert sugar and honey; polysaccharides including starch such as potato starch, corn starch and starch-based materials such as cereal flours (e.g. wheat flour, corn flour, malt flour, rice flour, rice bran), pectin and glycerol, hydrogenated monosaccharides and oligosaccharides (sugar alcohols) such as xylitol, sorbitol, mannitol, isomaltolose, trehalose and maltitol and syrups containing maltitol;

[0249] Preferred attractants are ethyl 3-methylbutyrate, methyl salicylate, amyl acetate, limonene or fruit extracts (e.g. apple extract made from dried and extracted apples, containing fructose, glucose, sorbitol, and flavorings of apples). Mixtures of attractants are also suitable.

[0250] In a further group of the examples, the organic active substances are organic active substances suitable for cosmetic applications or active mixtures in addition to the above-mentioned fragrances. Preferred cosmetic active substances for loading of the microparticles are especially active plant ingredients and plant extracts.

[0251] Examples of cosmetic active substances are skin and hair pigmentation agents, tanning agents, bleaching agents, keratin hardening substances, antimicrobial active ingredients, light-filtering active ingredients, repellent active ingredients, hyperemic substances, keratolytic and keratoplastic substances, antidandruff active ingredients, anti-inflammatory agents, keratinizing substances, antioxidant active ingredients and active ingredients acting as free radical scavengers, skin moisturizing or humectant substances, re-lubricating active ingredients, deodorant active ingredients, sebostatic active ingredients, plant extracts, anti-erythema or anti-allergic active ingredients and mixtures thereof.

[0252] Artificial tanning active substances suitable for tanning the skin in the absence of natural or artificial UV radiation are, for example, dihydroxyacetone, alloxan, and walnut shell extract. Suitable keratin hardening substances are usually active ingredients also used in antiperspirants, such as potassium alum, aluminum hydroxy chloride, aluminum lactate, etc. Antimicrobial active ingredients are used to destroy microorganisms and / or inhibit their growth and are thus used both as preservatives and also as deodorizing substances for reducing the formation or intensity of body odor. These include, for example, conventional preservatives known to those skilled in the art, such as parabens, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are, for example, zinc ricinoleate, triclosan, alkyl alkanolamide undecylenate, triethyl citrate, chlorhexidine, etc. Suitable light-filtering active ingredients are substances that absorb UV radiation in the UV-B and / or UV-A region. Suitable UV filters are those mentioned above. Also suitable are p-aminobenzoates, cinnamates, benzophenones, and camphor derivatives, as well as pigments that block UV radiation, such as titanium dioxide, talc, and zinc oxide. Suitable repellent active ingredients are compounds that are able to avoid or drive away certain animals, especially insects, from humans. These include, for example, 2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide, etc. Suitable hyperemic substances that stimulate blood flow through the skin are, for example, essential oils, such as dwarf pine, lavender, rosemary, juniper, roasted chestnut extract, birch leaf extract, hayseed extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc. Suitable keratolytic and keratoplastic substances are, for example, salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable antidandruff active ingredients are, for example, sulfur, sulfur polyoxyethylene sorbitan monooleate, sulfur ricinoleate polyethoxylate, zinc pyrithione, aluminum pyrithione, etc. Suitable anti-inflammatory agents against skin irritation are, for example, allantoin, bisabolol, Dragosantol, chamomile extract, panthenol, etc.

[0253] Other cosmetic active substances are aspalatin, glycyrrhizin, caffeine, proanthocyanidins, hesperetin, rutin, luteolin, polyphenols, oleuropein, theobromine, bioflavonoids, and polyphenols.

[0254] Examples of plant extracts are also acai extract (Euterpe oleracea), acerola extract (Malpighia glabra), wild horsetail extract (Equisetum arvense), Brazilian mushroom (Agaricus) extract (Agaricus blazei murill), aloe extract (Aloe vera, Aloe Barbadensis), apple extract (Malus), artichoke leaf extract (Cynara scolymus), artichoke flower extract (Cynara edulis), arnica extract (Arnica Montana), oyster extract (Ostrea edulis), valerian root extract (Valeriana officinalis), bearberry leaf extract (Arctostaphylos uva-ursi), bamboo extract (Bambusa vulgaris), bitter melon extract (Momordica charantia), bitter orange extract (Citrus aurantium), nettle leaf extract (Urtica dioica), nettle root extract (Urtica dioica), kale extract (Brassica oleracea), watercress extract (Rorippa nasturtium), coleus extract (Coleus forskohlii), capsicum extract (Capsicum frutescens), extract from centella asiatica (Gotu Kola), cinchona extract, cranberry extract (Vaccinium vitis-idaea), turmeric extract (Curcuma longa), damiana extract (Turnera diffusa), pitahaya extract, extract from echinacea, wheat placenta extract, edelweiss extract (Leontopodium alpinum), ivy extract (Hedera helix), tribulus extract (Tribulus terrestris), garcinia cambogia extract, ginkgo extract (Ginkgo biloba), ginseng extract (Panax ginseng), pomegranate extract (Punica granatum), grapefruit extract (Citrus paradisi), griffonia extract (Griffonia simplicifolia), green tea extract (Camellia sinensis), guarana extract (Paullinia cupana), cucumber extract (Cucumis sativus), dog rose extract (Rosacanina), blueberry extract (Vaccinium myrtillus), hibiscus extract (Malvacea), mallow extract, honey extract, hops extract (Humulus), ginger extract (Zingiber officinale), Iceland moss extract (Cetraria islandica), jojoba extract (Simmondsia chinensis), St. John's wort extract (Hypericum perforatum), coffee concentrate, cocoa bean extract (Theobroma cacao), cactus flower extract, chamomile flower extract (Matricaria recutita, Matricaria chamomila), carrot extract (Daucus carota), kiwi extract (Aperygidae), kudzu extract (Pueraria lobata), coconut milk extract, pumpkin seed extract (Curcurbita pepo), cornflower extract (Centaurea cyanus), lotus extract, dandelion extract (Taraxacum officinale), maca extract (Lepidium peruvianum), magnolia flower extract, mango extract, milk thistle extract (Silybum marianum), marigold extract (Calendula officiennalis), yerba mate extract (Hex paraguariensis), Podocarpus fleuryi extract (Rugcusaculeatus), seaweed extract, cranberry extract (Vaccinium macrocarpon), moringa extract, extract from musk mallow (Malva moschata), evening primrose oil extract (Azadirachta indica), nettle extract (Urticaceae), olive leaf extract (Olea europea), orange extract (hesperidin), orchid extract, papaya extract (Carica papaya), mint extract, extract from papaya (Geissospermum), bitter orange extract (Citrus aurantioum), bilberry extract (Vaccinium vitas-ideea), African cherry extract (Prunus africana), sugar beet extract, Japanese knotweed extract (Polygonum cuspidatum), rooibos extract (Aspalasthus Linnearis), rose flower extract, horse chestnut extract (Aesculus hippocastanum), rosemary extract (RosemarinusOfficinalis), red clover extract (Trifolium platense), red wine extract (Vitis vinifera), saw palmetto extract (Serenoa repens), lettuce extract (Lactuca sativa), sandalwood extract (Santalum rubrum), sage extract (Salvia officinalis), horsetail extract (Equisetum), yarrow extract (Achillea millefolium), black pepper extract (Piper nigrum), black tea extract, water lily extract (Nymphaea), white willow bark extract (Salix Alba), licorice extract (Glycyrrhiza), devil's claw extract (Harpagophytum procumbens), thyme extract (Thymus vulgaris), tomato extract (Lycopersicum esculentum), grape seed extract (Vitis vinifera), grape skin extract (Vitis vinifera), watercress (Rorippa amphibia), willow bark extract (Salix alba), wormwood extract (Artemisia absinthium), white tea extract, yam extract (Dioscorea opposita), yohimbine extract (Pausinystalia yohimbe), witch hazel extract (Hamamelis), cinnamon extract (Cinnamomum cassia Presl), lemon extract (Citrus), and onion extract (Allium cepa).

[0255] In a further group of the examples, the low molecular weight organic active substances are vitamins, in particular lipophilic vitamins such as vitamin A, vitamin D, vitamin E or vitamin K or combinations thereof.

[0256] In a further group of the examples, the low molecular weight organic active substances are organic effect compounds. Effect compounds are organic active substances that do not belong to agrochemicals, fragrance chemicals, vitamins, AIPs, and cosmetic active substances. The group of effect compounds is typically not permitted for use in agriculture, for application to humans, for cosmetic or dietary purposes. They include, but are not limited to, compounds for construction chemistry, in particular catalysts, and also dyes, UV stabilizers, polymerization inhibitors, oxidation stabilizers, etc. Preferred active substances for encapsulation into microparticles for use in construction chemistry are especially polymerization catalysts.

[0257] Available polymerization catalysts include those suitable for curing reactive resins, especially addition resins, condensation resins or oxidation-curing resins. For this purpose, the polymerization catalysts are catalysts for free radical polymerization, polycondensation and / or polyaddition. Suitable catalysts for free radical polymerization include, in particular, peroxide splitters and catalysts known from coating technology for oxidative drying oils and alkyd resins as driers or siccatives. Suitable polycondensation catalysts are catalysts for silicone condensation and crosslinking. The polyaddition catalysts used can be, for example, catalysts for curing epoxy resins. In addition, the polyaddition catalysts used can be, for example, urethanization catalysts customarily used in polyurethane chemistry. These are compounds that accelerate the reaction of the reactive hydrogen atoms of isocyanate-reactive components with organic polyisocyanates.

[0258] Available polymerization catalysts include, in particular, tertiary amines, phosphines and organometallic salts.

[0259] Tertiary amines that can be used as polymerization catalysts, especially for polyaddition, are, for example, triethylamine, tributylamine, N,N-dimethylcyclohexylamine (DMCHA), N-methylbicyclohexylamine, N,N-dimethylbenzylamine (BDMA), N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, 2,2'-dimorpholinodiethylether (DMDEE), N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N”-pentamethyldiethylenetriamine (PMDETA), N,N,N',N”-pentamethyldipropylenetriamine (PMDPTA), N,N,N-tris(3-dimethylaminopropyl)amine, bis(2-dimethylaminoethyl)ether (BDMAEE), bis(dimethylaminopropyl)urea, 2,4,6-tris(dimethylaminomethyl)phenol and its salts with 2-ethylhexanoic acid and its isomers, 1,4-dimethylpiperazine (DMP), N-methylimidazole, 1,2-dimethylimidazole, 1-methyl-4-(2-dimethylaminoethyl)piperazine, 1-azabicyclo[3.3.0]octane, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-7-ene (DBN).

[0260] Further available polymerization catalysts, especially for polyaddition, include: tris(dialkylamino)-s-hexahydrotriazines, especially 1,3,5-tris(3-[dimethylamino]propyl)hexahydrotriazine.

[0261] Phosphines which are useful as polymerization catalysts, especially for polyaddition, are preferably tertiary phosphines such as triphenylphosphine or methyldiphenylphosphine.

[0262] The organometallic salts which can be used as polymerization catalysts preferably have the general formula

[0263] L m M n+ n A -

[0264] where

[0265] the ligand L is an organic group or organic compound selected from alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl and acyl, the ligand L has from 1 to 20 carbon atoms, and m ligands L are the same or different,

[0266] m is 0, 1, 2, 3, 4, 5 or 6,

[0267] M is a metal,

[0268] n is 1, 2, 3 or 4, and

[0269] the anion A - is a carboxylate ion, an alkoxide ion or an enolate ion.

[0270] The metal M is preferably selected from lithium, potassium, cesium, magnesium, calcium, strontium, barium, boron, aluminum, indium, tin, lead, bismuth, cerium, cobalt, iron, copper, lanthanum, manganese, mercury, scandium, titanium, zinc and zirconium; more particularly from lithium, potassium, cesium, tin, bismuth, titanium, zinc and zirconium.

[0271] The ligand L is preferably an alkyl group having from 1 to 20 carbon atoms. More preferably, L is an alkyl group having from 1 to 10 carbon atoms, especially from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

[0272] The carboxylate ion preferably has the formula R 1 -COO - where R 1 is selected from H, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl and acyl, and where the R 1 group has up to 20 carbon atoms, preferably from 6 to 20 carbon atoms. Particularly preferred carboxylate ions are selected from the anions of natural and synthetic fatty acids, such as neodecanoate, isooctanoate and laurate, and the anions of resin acids and naphthenic acids.

[0273] The enolate ion preferably has R 2 CH=CR 3 -O -, where R 2 and R 3 are each independently selected from H, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl and acyl, and where R 2 and R 3 groups each have up to 20 carbon atoms. Specific examples are ethyl pyruvate, heptyl pyruvate or phenyl pyruvate. The enolate ion is preferably derived from a 1,3-diketone having five to eight carbon atoms. Possible examples include acetylacetonate, the enolate of 2,4-hexanedione, the enolate of 3,5-heptanedione and the enolate of 3,5-octanedione.

[0274] The alkoxide ion preferably has the formula R 4 -O - , where R 4 is selected from alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl and acyl, and where R 4 group has up to 20 carbon atoms.

[0275] In a specific embodiment, the organometallic compound is selected from

[0276] - alkali metal carboxylates such as lithium 2-ethylhexanoate, lithium neodecanoate, potassium acetate, potassium 2-ethylhexanoate, cesium 2-ethylhexanoate;

[0277] - alkaline earth metal carboxylates such as calcium 2-ethylhexanoate, calcium naphthenate, calcium octanoate (available as Calcium from OMG Borchers), magnesium stearate, strontium 2-ethylhexanoate, barium 2-ethylhexanoate, barium naphthenate, barium neodecanoate;

[0278] - aluminum compounds such as aluminum acetylacetonate, aluminum dionate (e.g. K 5218 from King Industries);

[0279] - zinc compounds such as zinc(II) diacetate, zinc(II) 2-ethylhexanoate and zinc(II) octanoate, zinc neodecanoate, zinc acetylacetonate;

[0280] - Tin compounds such as tin(II) carboxylates, examples being tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, tin(II) neodecanoate, tin(II) isononanoate, tin(II) laurate, and dialkyltin(IV) salts of organic carboxylic acids, examples being dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate, and dioctyltin diacetate, especially dibutyltin dilaurate;

[0281] - Titanium compounds such as tetra(2-ethylhexyl) titanate;

[0282] - Zirconium compounds such as zirconium ethylhexanoate, zirconium neodecanoate, zirconium acetylacetonate (e.g., K- 4205 from King Industries); zirconium bis(acetylacetonate) (e.g., XC-9213; XC-A 209 and XC-6212 from King Industries);

[0283] - Bismuth compounds such as bismuth carboxylates, especially bismuth octoate, bismuth ethylhexanoate, bismuth neodecanoate, or bismuth pivalate (e.g., 348, XC-B221, XC-C227, XC 8203, XK 651 from King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 from TIB Chemicals, and those from Shepherd Lausanne);

[0284] - Manganese salts such as manganese neodecanoate, manganese naphthenate;

[0285] - Cobalt salts such as cobalt neodecanoate, cobalt ethylhexanoate, cobalt naphthenate;

[0286] - Iron salts such as iron ethylhexanoate;

[0287] - Mercury compounds such as phenylmercury carboxylate.

[0288] Preferred organometallic compounds are dibutyltin dilaurate, dioctyltin dilaurate, zinc(II) diacetate, zinc(II) dioctoate, zirconium acetylacetonate, and zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate, bismuth neodecanoate, bismuth dioctoate, and bismuth ethylhexanoate.

[0289] In a preferred group of embodiments, the aqueous emulsion is an oil-in-water emulsion (o / w emulsion) of a water-immiscible liquid, wherein the water-immiscible liquid contains at least one organic active compound which is preferably a biocide.

[0290] Particularly preferred is an oil-in-water (o / w) emulsion, in which the droplets of the o / w emulsion are formed from a liquid immiscible with water and these droplets are surrounded by at least one conjugate as defined herein.

[0291] Suitable water-immiscible liquids (water-immiscible solvents) for dissolving organic active compounds are mainly any organic solvent or solvent mixture having a solubility of not more than 50 g / l or not more than 20 g / l, in particular not more than 10 g / l, in deionized water.

[0292] Suitable water-immiscible liquids (water-immiscible solvents) for dissolving organic active compounds, in particular biocides, are in particular hydrocarbon solvents having a boiling point of at least 100 °C, C8-C 26 -alkyl esters of C1-C8-fatty acids, C8-C 26 -mono- and di-C1-C4-alkylamides of C8-C-fatty acids, N-C5-C 18 -alkylpyrrolidones and mixtures thereof. Among these, preference is given to solvents and solvent mixtures which are liquid at 20 °C.

[0293] In this context, "liquid" means that the diluent has a dynamic viscosity (determined as described in ASTM D 445) of generally not more than 150 mPa·s, in particular not more than 100 mPa·s, specifically not more than 50 mPa·s, in particular in the range from 1 to 150 mPa·s, preferably in the range from 2 to 100 mPa·s and in particular in the range from 3 to 50 mPa·s at 20 °C under standard conditions.

[0294] In this context, aliphatic hydrocarbon solvents having a boiling point of at least 100 °C are in particular those having a boiling point in the said range and containing 7 to about 18 carbon atoms, which may optionally contain non-aromatic carbocycles, and which are saturated and unsaturated hydrocarbons (such as straight-chain, branched-chain and cyclic alkanes and alkenes), and in particular mixtures of these aliphatic hydrocarbons. Such mixtures are commercially available, for example, under the trade name Exxsol, which denotes products mainly containing kerosene from which the aromatic components have been removed, such as Exxsol TM D30, Exxsol TM D40, Exxsol TM D80, Exxsol TM D100, Exxsol TM D120 and Exxsol TM D220 / 230. An example of an aliphatic hydrocarbon having a carbocycle is limonene.

[0295] In the context of the present invention, aromatic hydrocarbon solvents having a boiling point of at least 100 °C particularly refer to monocyclic or polycyclic aromatic compounds which may optionally carry one or more aliphatic or araliphatic substituents, in particular alkyl and arylalkyl moieties, and have a boiling point within said range. The aromatic hydrocarbon solvents preferably refer to mixtures of such aromatic compounds which are particularly obtained from crude oil products by distillation into fractions within a given boiling point range, such fractions being commercial products known under the following trade names: In particular 100, 150, 200, 150 ND and 200 ND; In particular 150 and 200; In particular A 200 and A 230 / 270; In particular 20 and 28; Aromat K 150, Aromat K200; In particular A 100 and A150; and Fin FAS-TX, in particular Fin FAS-TX 150 and Fin FAS-TX 200. Mixtures which are particularly preferably free of the potentially carcinogenic substance naphthalene 150 ND and 200 ND (ExxonMobil Chemical). Thus, 150 ND mainly contains aromatic hydrocarbons having 10 or 11 carbon atoms which boil in the range from 175 °C to 209 °C and mainly consists of alkylbenzenes, while 200 ND mainly contains aromatic hydrocarbons having 10 to 14 carbon atoms which boil in the range from 235 °C to 305 °C and mainly consists of alkylnaphthalenes.

[0296] Another example of the aromatic hydrocarbon solvent is a product known under the trade name Hisol SAS-296, which consists of a mixture of 1-phenyl-1-dimethylphenylethane and 1-phenyl-1-ethylphenylethane.

[0297] In the context of C8-C 26 -alkyl esters of C1-C8-fatty acids and mono- and di-C1-C4-alkylamides of C8-C 26 -fatty acids, the term "C8-C26 "-fatty acid" means a fatty acid or a mixture of fatty acids having 8 to 26 carbon atoms. C8-C 26 -Examples of fatty acids are the saturated fatty acids caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid; the monounsaturated fatty acids undecenoic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, eicosenoic acid, cetoleic acid, erucic acid and nervonic acid; and the polyunsaturated fatty acids linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, clupanodonic acid and cervonic acid.

[0298] Among the C1-C8-alkyl esters of C8-C 26 -fatty acids, preference is given to C1-C4-alkyl esters, in particular C 12 -C 22 -alkyl esters of C8-C fatty acids, especially C 12 -C 22 -methyl and ethyl esters of C8-C fatty acids. Preference is given to C 12 -C 22 -alkyl esters of C8-C fatty acids, in which the total amount of saturated or monounsaturated C 12 -C 22 -fatty acids is at least 80% by weight based on the total weight of the fatty acids in the fatty acid ester. In particular, the C1-C8-alkyl esters of C8-C 26 -fatty acids are methylated or ethylated vegetable oils, i.e. products obtained by transesterification of vegetable oils with methanol or ethanol.

[0299] Among the mono- and di-C1-C4-alkylamides of C8-C 26 -fatty acids, preference is given to C 12 -C 22 -mono- and di-C1-C4-alkylamides of C8-C fatty acids, especially their mono-methylamide, mono-ethylamide, dimethylamide and diethylamide. Particular preference is given to C 12 -C 22 -mono- and di-C1-C2-alkylamides of C8-C fatty acids, in which the total amount of saturated or monounsaturated C 12 -C 22 -fatty acids is at least 80% by weight based on the total weight of the fatty acids in the mono- and di-C1-C2-alkylamides of C 12 -C 22 -fatty acids. Mixtures of methyl esters of saturated and monounsaturated C 14 -C 18 -fatty acids are available, for example, under the trade name SynativeTM ESME TI 05 (Cognis) is commercially available.

[0300] N-C5-C 18 Examples of N-alkylpyrrolidones are N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-isopropylpyrrolidone, N-butylpyrrolidone, N-isobutylpyrrolidone, N-pentylpyrrolidone, N-hexylpyrrolidone, N-(4-ethyl-pentyl)pyrrolidone, N-octylpyrrolidone, N-2-ethylhexylpyrrolidone, N-nonylpyrrolidone, N-decylpyrrolidone and N-(7-methyl-decyl)pyrrolidone, n-dodecylpyrrolidone and N-tetradecylpyrrolidone.

[0301] The aqueous compositions of the invention containing at least one agrochemical, in particular a pest control agent, are particularly suitable for controlling phytopathogenic organisms or for controlling the growth of plants. Thus, the use of the aqueous compositions of the invention containing at least one agrochemical, in particular a pest control agent, for controlling phytopathogenic organisms or for controlling the growth of plants is particularly preferred.

[0302] In the aqueous compositions of the invention, the relative amount of the conjugate is generally in the range from 1% to 50% by weight, in particular in the range from 2% to 40% by weight, more particularly in the range from 3% to 35% by weight and especially in the range from 5% to 30% by weight, based on the weight of the water-immiscible liquid.

[0303] In a specific group of the examples, the aqueous composition is an aqueous oil-in-water emulsion (o / w emulsion). In the o / w emulsion, the amount of the oil phase can be in the range from 0.1% to 60% by weight, in particular in the range from 1% to 50% by weight, especially in the range from 1.5% to 40% by weight, based on the total weight of the emulsion.

[0304] The conjugates of the invention can also be used in applications where stabilization of aqueous emulsions, in particular oil-in-water emulsions, and / or stabilization of oily dirt is required. Thus, the conjugates of the invention can also be used as surfactants in surfactant-containing compositions such as washing and cleaning compositions, including liquid and solid laundry detergents, dishwashing detergents (including machine dishwashing compositions and hand dishwashing detergents), and cleaning compositions (cleaners) such as household and industrial cleaners and hard surface cleaners. In these compositions, the conjugates can replace a part of the conventional surfactants contained therein and thus improve the ecological compatibility of these compositions.

[0305] Example

[0306] The present invention will be described in more detail by way of examples given below.

[0307] Materials:

[0308] -CT-COOH: 5-((3,7-dimethyloct-6-en-1-yl)oxy)-5-oxopentanoic acid

[0309] -MT-COOH: 5-((2-isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid

[0310] -THG-COOH: 5-((3,7-dimethyloctyl)oxy)-5-oxopentanoic acid

[0311] - H: Polycitronellol. 3,7-dimethyl-6-octen-1-ol homopolymer. CAS = 888224-71-3. P2 Science

[0312] -Novozyme 435: Immobilized lipase. Novozymes

[0313] -Dextran 4: Anhydroglucose. CAS = 9004-54-0. Serva Electrophoresis GmbH

[0314] -Dextran-NH2: Reaction product between Dextran 4 and hexamethylenediamine

[0315] -DMSO: Dimethyl sulfoxide. CAS = 67-68-5

[0316] -THF: Tetrahydrofuran. CAS = 109-99-9

[0317] -Cinmethylin: exo-(±)-1-methyl-2-(2-methylbenzyloxy)-4-isopropyl-7-oxabicyclo[2.2.1]heptane. BASF

[0318] -Xanthan gum: Xanthan gum, G, Solvay S.A.

[0319] Synthesis

[0320] (1) Synthesis of terpene derivatives

[0321] Example 1:

[0322] Synthesis of 5-((3,7-dimethyloct-6-en-1-yl)oxy)-5-oxopentanoic acid (CT-COOH)

[0323] The synthesis is carried out in two steps: esterification (i), followed by transesterification (ii).

[0324] (i) Esterification: Glutaric acid (1.00 g, 7.57 mmol), citronellol (2.36 g, 15.14 mmol), Novozyme 435 (0.169 g) and 8 mL of 2-methylbutan-2-ol solvent were added to a 25 mL round-bottom flask equipped with a magnetic stirrer. The flask was sealed and the reaction mixture was stirred at 40 °C (170 rpm) for 6 h, resulting in the formation of bis(3,7-dimethyloct-6-en-1-yl) glutarate. After completion of the reaction, the mixture was filtered and the solvent was evaporated under a rotary evaporator to give 1.86 g of bis(3,7-dimethyloct-6-en-1-yl) glutarate.

[0325] (ii) Transesterification: Glutaric acid (2.00 g, 15.14 mmol), bis(3,7-dimethyloct-6-en-1-yl) glutarate (6.19 g, 15.14 mmol) and a few drops of concentrated H2SO4 (catalytic amount) were added to a 25 mL round-bottom flask equipped with a magnetic stirrer. The flask was sealed and the reaction mixture was stirred overnight at 100 °C. The monoester was purified by column chromatography using a mixture of hexane:ethyl acetate (90:10) as the mobile phase. 3.32 g of the transesterified monoester 5-((3,7-dimethyloct-6-en-1-yl)oxy)-5-oxopentanoic acid (CT-COOH) was obtained.

[0326] Example 2:

[0327] Synthesis of 5-((2-isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid (MT-COOH)

[0328] 5-((2-Isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid was prepared using the same two-step procedure as in Example 1.

[0329] (i) Esterification: Menthol (2.36 g, 15.14 mmol) was used instead of citronellol, and 1.92 g of bis(2-isopropyl-5-methylcyclohexyl) glutarate was obtained.

[0330] (ii) Transesterification: Bis(2-isopropyl-5-methylcyclohexyl) glutarate (6.19 g, 15.14 mmol) was used instead of bis(3,7-dimethyloct-6-en-1-yl) glutarate, and 1.98 g of 5-((2-isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid (MT-COOH) was obtained.

[0331] Example 3: Synthesis of 5-((3,7-dimethyloctyl)oxy)-5-oxopentanoic acid (THG-COOH)

[0332] The same two-step procedure as in Example 1 was used to make 5-((2-isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid.

[0333] (i) Esterification: Tetrahydrogeraniol (2.40 g, 15.14 mmol) was used instead of citronellol, and 2.01 g of bis(3,7-dimethyloctyl) glutarate was obtained.

[0334] (ii) Transesterification: Bis(3,7-dimethyloctyl) glutarate (6.25 g, 15.14 mmol) was used instead of bis(3,7-dimethyloct-6-en-1-yl) glutarate, and 2.02 g of 5-((3,7-dimethyloctyl)oxy)-5-oxopentanoic acid (THG-COOH) was obtained.

[0335] Example 4: Synthesis of Citropol-COOH

[0336] 21.12 g of glutaric acid, 10 g of H, 1.55 g of Novozyme 435, 20 g of dry molecular sieve, and 45 mL of 2-methylbutan-2-ol solvent were added to a 250 mL round-bottom flask equipped with a magnetic stirrer. The flask was sealed and the reaction mixture was stirred (170 rpm) at 40 °C for 16 h, resulting in the formation of Citropol-COOH. After the reaction was completed, the mixture was filtered and the solvent was evaporated under a rotary evaporator. Then the crude mixture was dissolved in 100 mL and dropped into 600 mL of water to obtain phase separation of the desired material layer. The oil phase was dried over sodium sulfate and evaporated to yield 7.5 g of Citropol-COOH.

[0337] (2) Modification of dextran with terpene derivatives

[0338] Example 5: Synthesis of dextran-grafted-citronellol

[0339] Dextran 4 (0.25 g), CT-COOH (0.25 g, 9.2×10-4 mol), and 3 mL of dry DMSO were added to a 10 mL round-bottom flask equipped with a magnetic stirrer. The mixture was stirred to obtain a homogeneous solution. Then Novozyme 435 (0.125 g) and dry molecular sieve (1.0 g) were added, and the flask was sealed. The reaction mixture was heated and stirred at 40 °C with stirring (170 rpm) for 24 h. After the reaction, the modified dextran was precipitated three times in acetone to remove free terpenes. After the drying process, 0.16 g of the dextran-grafted-citronellol amphiphilic polymer was recovered as a powder.

[0340] Example 6: Synthesis of Dextran-grafted-Menthol

[0341] The same procedure as in Example 5 was used to produce dextran-grafted-menthol.

[0342] Only the differences in raw materials or amounts used are listed here. MT-COOH (0.50 g, 1.85 mmol) was used instead of CT-COOH. 5 mL of dry DMSO, 0.625 g of Novozyme 435, and 3 g of dry molecular sieves were added. After the drying process, 0.20 g of the dextran-grafted-menthol polymer was recovered as a powder.

[0343] The biodegradation of the compound in soil was evaluated using sandy soil Lihof C15 under ISO 17556 specifications. The percentage of biodegradation was determined by the release of CO2 generated during mineralization. After 28 days and 90 days, 72% and 85% biodegradation were found, respectively.

[0344] Example 7: Synthesis of Dextran-grafted-Citropol

[0345] Dextran 4 (0.40 g), Citropol-COOH (Example 4, 0.80 g), and 10 mL of dry DMSO were added to a 25 mL round-bottom flask equipped with a magnetic stirrer. The mixture was stirred to obtain a homogeneous solution. Then, Novozyme 435 (0.30 g) and dry molecular sieves (1.60 g) were added, and the flask was sealed. The reaction mixture was heated with stirring (170 rpm) at 40 °C for 24 h. After the reaction, the modified dextran was precipitated three times in methanol to remove unreacted Citropol derivatives. After the drying process, 0.34 g of the dextran-grafted-Citropol amphiphilic polymer was recovered as a waxy solid.

[0346] The biodegradation of the compound in soil was evaluated using sandy soil Lihof C15 under ISO 17556 specifications. The percentage of biodegradation was determined by the release of CO2 generated during mineralization. After 28 days and 90 days, 59% and 75% biodegradation were found, respectively.

[0347] Example 8: Synthesis of Dextran-block-Citropol

[0348] The synthesis was carried out in two steps: amination (i), followed by amidification (ii).

[0349] (i) Amination: In a 10 mL round-bottom flask equipped with a magnetic stirrer, add dextran 4 (1.00 g), hexamethylenediamine (112 g, 9.63 mmol) and 2 mL of water. Stir the mixture for 2 hours. After that, add sodium cyanoborohydride (0.125 g, 1.99 mmol).

[0350] Seal the flask and stir the reaction mixture at room temperature (170 rpm) overnight. Precipitate the medium twice in acetone and dry to obtain 0.91 g of end-group aminated dextran (dextran-NH2).

[0351] (ii) Amidation: In a 25 mL round-bottom flask equipped with a magnetic stirrer, add dextran-NH2 (0.40 g), Citropol-COOH (Example 4, 0.80 g) and 6 mL of dry DMSO. After mixing, add Novozyme 435 (0.15 g) and dry molecular sieve (1.00 g) to the solution. Seal the flask and stir the reaction mixture at 40 °C for 24 hours. After the reaction, precipitate the modified dextran three times in methanol to remove the unreacted Citropol derivatives. After the drying process, 0.32 g of dextran-block-Citropol amphiphilic polymer is recovered as a powder.

[0352] (3) Emulsion stability

[0353] Example 9: Preparation of a cinmethylin liquid emulsion containing dextran-grafted-menthol

[0354] Add 7.00 g of distilled water and 0.60 g of dextran-grafted-menthol produced as in Example 6 to a plastic vial. Stir the medium to assist in polymer dissolution. Then add 2.40 g of cinmethylin and place the vial in an ice bath. Then use an ultrasonic homogenizer UP400S (Hielscher Ultrasonics) to subject the mixture to high shear for 1 min at 80% amplitude using 0.5 cycles.

[0355] A uniform emulsion with a droplet diameter D[3,2] = 2.8 μm is obtained. No phase separation or stratification is observed within 24 hours.

[0356] Example 10:

[0357] Preparation of a cinmethylin liquid emulsion containing dextran-grafted-citropol

[0358] Add 0.085 g of cinmethylin and 0.015 g of dextran-grafted-citropol (synthesized as in Example 7) and 9.90 g of phosphate buffer (pH 6 0.5 M) to a plastic vial. Finally, blend the mixture with an Ultraturax for 5 min and obtain a white emulsion.

[0359] No phase separation or turbidity change was observed within 72 hours.

[0360] Example 11: Preparation of a cinmethylin liquid emulsion containing hydrophilic dextran (comparative example)

[0361] Add 1 g of cinmethylin and 0.10 g of unmodified dextran 4 and 9.00 g of phosphate buffer (pH 5.8 0.5 M) to a plastic vial. Place the mixture in an ice bath and then subject it to high shear for 5 min with an ultrasonic homogenizer Vibra Cell 72408 at 30% amplitude. A stable emulsion could not be achieved and complete stratification was found within a few hours.

[0362] (4) Herbicidal activity of the cinmethylin liquid emulsion according to the present invention

[0363] The herbicidal activities of the following cinmethylin liquid emulsions according to the present invention were evaluated. These emulsions are designated as Formulations 1 and 2 herein (also designated as F1 and F2 below) and have the compositions shown in Table 1.

[0364] Table 1: Compositions of Formulations 1 and 2

[0365] Composition Formulation 1 Formulation 2 Cinmethylin 30% by weight 30% by weight Dextran-grafted-menthol 5.3% by weight 10% by weight Xanthan gum 0.2% by weight 0.2% by weight Water 64.5% by weight 59.8% by weight

[0366] According to the procedure of Example 9, Formulations 1 and 2 were prepared using the amounts shown in Table 1. As another exception, water was initially mixed not only with dextran-grafted menthol but also with xanthan gum in the amounts indicated in Table 1.

[0367] The herbicidal activities of Formulations 1 and 2 against various weeds and against crops were demonstrated by the following pre-emergence treatment greenhouse experiments. For this purpose, Formulations 1 and 2 of the present invention and a conventional cinmethylin formulation were applied and the herbicidal effects of these treatments were compared.

[0368] Test plants were inoculated in sandy loam containing 5% organic matter in plastic containers. For pre-emergence treatment, after sowing, Formulations 1 and 2 and two conventional formulations for comparison purposes, namely a polyurea capsule suspension (CS) and an emulsifiable concentrate (EC) containing 400 g / l and 750 g / l of cinmethylin respectively, were each directly applied at application rates of 100, 50, 25 and 12.5 g a.i. / ha (a.i. = active ingredient, here cinmethylin) by means of a fine distribution nozzle. The containers were gently irrigated to promote germination and growth and then covered with a transparent plastic lid until the plants had rooted. This covering ensured uniform germination of the test plants, unless this was adversely affected by the active compound. The plants were cultivated at 10 °C to 35 °C according to their individual requirements.

[0369] The herbicidal activity of the individual herbicidal formulations was evaluated 10 and 20 days after treatment (10 and 20 DAT). The results are summarized in Table 2. The damage to the unwanted weeds and crop plants caused by these formulations was evaluated using a scale from 0% to 100% compared to untreated control plants. Here, 0% means no damage and 100% means complete destruction of the plants.

[0370] The plants used in the greenhouse tests belonged to the following species:

[0371] EPPO code Scientific name ALOMY Alopecurus myosuroides LOLRI Lolium rigidum LOLMU Lolium multiflorum TRZAW* Soft wheat (winter) HORVW* Barley (winter)

[0372] * Crop plants (for selectivity testing)

[0373] Table 2 Pre-emergence application of Formulations F1 and F2 according to the invention and conventional CS and EC formulations:

[0374]

[0375]

[0376] 1) Formulations F1 and F2 according to the invention

[0377] 2) Comparative CS and EC formulations

[0378] As can be seen from the results summarized in Table 2, compared to the conventional cinmethylin formulations, Formulations F1 and F2 according to the invention exhibit increased or at least similar activity against weeds and also exhibit increased or at least similar weed selectivity relative to the crop.

Claims

1. A conjugate of a sugar compound and at least one hydrophobic compound, wherein the sugar compound is selected from disaccharides, oligosaccharides and polysaccharides, and the at least one hydrophobic compound is selected from terpenes, polyterpenes and polyterpene ethers, wherein the hydrophobic compound in the conjugate is directly bound to an oxygen atom of the sugar or is present as a group having formula (I) or (II): R-O-(Y) k -A 1 -X 1 -(I) R-O-(Y) k -A 1 -X 2 -A 2 -X 3 -(II) wherein in formula (I) and (II) R is a group of a terpene compound, polyterpene or polyterpene ether compound, k is 0 or 1, Y is C(O) or C(O)NH, A 1 is a direct bond or a C1-C6 alkylene group, A 2 is a C2-C 10 alkylene group, X 1 is C(O), or, if k = 1 and A 1 is C1-C6 alkylene, may also be OC(O) or NHC(O), and wherein X 1 is attached to the oxygen atom of the saccharide compound X 2 is C(O)NH or NHC(O)NH, X 3 - is N= or NH-, and wherein X in formula (II) 3 is attached to a carbon atom of the saccharide compound.

2. The conjugate according to claim 1, wherein the sugar compound of the conjugate has at least one of the following properties 2.a to 2.d: 2.a It has a number average of 2 to 1000 monosaccharide repeating units. 2.b It is a non-ionic polysaccharide; 2.c It is dextran 2.d It is selected from dextran, pullulan, dextrin and combinations thereof.

3. The conjugate according to any one of the preceding claims, wherein, The hydrophobic compound is selected from monoterpenols, sesquiterpenols and diterpenols, oxidized monoterpenols, oxidized sesquiterpenols and oxidized diterpenols, and polyterpene ether compounds, wherein the terpene units of the polyterpene ether compounds are derived from monoterpenols, sesquiterpenols and diterpenols.

4. The conjugate according to claim 3, wherein, The hydrophobic compound is selected from monoterpenols, sesquiterpenols, oxidized monoterpenols and oxidized sesquiterpenols.

5. The conjugate according to claim 3 or 4, wherein The hydrophobic compound is a terpene alcohol, and the terpene alcohol is selected from citronellol, nerol, geraniol, myrcenol, bulnesol, menthol and combinations thereof.

6. The conjugate according to any one of the preceding claims, having at least one of the following properties 5.a or 5.b: 5.a The weight ratio of the hydrophobic compound to the sugar compound in the conjugate is in the range of 3:1 to 1:80, particularly in the range of 2:1 to 1:60; 5.b The conjugate has a degree of substitution of the hydrophobic compound in the range of 1 to 300 mol-% relative to the monosaccharide units of the sugar.

7. The conjugate according to any one of the preceding claims, wherein, In the conjugate, the hydrophobic compound is directly bound to an oxygen atom of the sugar or is present as a group having formula (I).

8. The conjugate according to any one of claims 1 to 6, wherein The hydrophobic compound is present as a group having formula (II), wherein R in formula (II) is particularly a polyterpene ether group.

9. Use of the conjugate according to any one of the preceding claims as a stabilizer for an aqueous emulsion of a water-immiscible liquid.

10. An aqueous composition which is an aqueous emulsion of a water-immiscible liquid, the aqueous emulsion containing at least one conjugate according to any one of claims 1 to 7.

11. The use or composition according to any one of claims 9 or 10, wherein, The weight ratio of the conjugate to the water-immiscible liquid of the emulsion is in the range of 1:100 to 1:1, particularly in the range of 1:50 to 1:2, especially in the range of 1:30 to 1:

3.

12. Use or composition according to any one of claims 9 to 11, wherein, The water-immiscible liquid contains at least one organic active compound.

13. The use or composition according to claim 12, wherein The organic active compound is a water-immiscible liquid at 22 °C and / or is dissolved in a water-immiscible organic solvent.

14. The use or composition according to any one of claims 12 or 13, wherein The organic active compound is selected from agrochemicals, aroma chemicals, pharmaceutically active compounds, vitamins, cosmetic active substances and organic effect compounds.

15. The use or composition according to any one of claims 12 to 14, which is an oil-in-water (o / w) emulsion, wherein, The droplets of the o / w emulsion are formed from the water-immiscible liquid and are surrounded by at least one conjugate as described in any one of claims 1 to 8.

16. The use or composition according to any one of claims 9 to 15, wherein, The relative amount of the conjugate is in the range of 1% to 50% by weight based on the weight of the water-immiscible liquid.

17. A method for stabilizing an aqueous emulsion, in particular an oil-in-water emulsion, of a water-immiscible liquid, the method comprising incorporating a conjugate as described in any one of claims 1 to 8 into the emulsion of the water-immiscible liquid.

18. Use of a composition as described in any one of claims 10 to 16 for controlling phytopathogenic organisms or for controlling plant growth, the composition containing at least one agrochemical.

19. A method for controlling phytopathogenic organisms, the method comprising the steps of: Applying a pesticidally effective amount of a composition as described in any one of claims 10 to 16 to the phytopathogenic organisms, or to the habitat of the phytopathogenic organisms, or to plants whose growth is to be controlled, the composition containing at least one agrochemical.

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