Process for preparing organosilicon compounds

Abstract

The present invention relates to a process for preparing organosilicon compounds and to the use of the compounds thus obtained.

Description

[Technical field]

[0001] The present invention relates to a process for preparing organosilicon compounds and to the use of the compounds thus obtained. [Background technology]

[0002] Polysiloxanes are known as components of hydraulic fluids meeting the US Department of Traffic DOT5 standard and certain brake fluids.

[0003] US Pat. No. 3,814,691 describes the preparation of such organosilanes by reacting the corresponding alkylsilyl chloride with the desired alcohol, which can be a glycol ether.

[0004] However, a drawback of the organosilanes obtained by this reaction is the residual chloride content, which can cause corrosion in hydraulic systems and can lead to leaks under the high pressures prevailing in these systems.

[0005] EP 557027 A1 describes a multi-step process in which polysiloxanes are first reacted with alcohols in the presence of a catalyst, the catalyst is removed, and then reacted with glycols and glycol ethers.

[0006] A disadvantage of this reaction scheme is that in the first reaction step a high proportion of high molecular weight residues is formed which are not available for reaction with glycols and glycol ethers.

[0007] US 2015 / 0221986A1 describes the preparation of organosilicon compounds by reacting various alkoxyalkanols with, for example, hexamethylcyclotrisilazane or alkoxysilanes.The disadvantage of preparing from hexamethylcyclotrisilazane is the high chlorine content associated with this preparation method. Summary of the Invention [Problem to be solved by the invention]

[0008] The objective was to provide a method for preparing chlorine-free organosilicon compounds, which allows the product to be obtained in high yield and purity, so that the reaction mixture is as easy as possible for use in its application. [Means for solving the problem]

[0009] The object of this invention is to provide a compound of formula (III) (III)R 1 x Si(-[-O-CH2-CH2-] n -OR 3 ) 4-x This is achieved by a process for preparing an organosilicon compound or mixture thereof of formula (Ia) (Ia)R 1 x Si(OR 2 ) 4-x and / or at least one alkoxyalkylsilane of formula (Ib) (Ib)-(-SiR 1 2-O-) y - The cyclic siloxane of formula (II) (II)R 3 -O-[-CH2-CH2-O-] n -H in the presence of at least one acid or at least one base, optionally in a solvent, at a temperature between 0 and 200° C., wherein R 1 is phenyl or C1-C4 alkyl, preferably C1-C4 alkyl, more preferably methyl, ethyl or n-butyl, most preferably methyl or ethyl; R 2 is C1-C4 alkyl, more preferably methyl, ethyl or n-butyl, most preferably methyl or ethyl; R 3is C1-C4 alkyl, more preferably methyl, ethyl or n-butyl; x is a positive integer 1, 2, or 3; y is a positive integer 3 or 4, preferably 3; and n is a positive integer of 2 to 5, preferably 2 to 4, more preferably 2 or 3, and most preferably 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Formula (Ia) (Ia)R 1 x Si(OR 2 ) 4-x The starting compound may be a monoalkoxytrialkylsilane (x=3), a dialkoxydialkylsilane (x=2), a trialkoxymonoalkylsilane (x=1) or a mixture thereof. 1 When is phenyl, these are the corresponding monoalkoxytriphenylsilanes, dialkoxydiphenylsilanes, and trialkoxymonophenylsilanes, respectively.

[0011] For simplicity, compounds of formula (Ia) may be represented by the radical R 1 Even when the aryl group contains a phenyl group, the aryl group is referred to as an alkoxyalkylsilane in this specification.

[0012] When the compound of formula (Ia) is used in the form of a mixture, the organosilicon compound of formula (III) is also obtained in the form of a mixture. The ratio of the compounds of formula (Ia) here generally corresponds to the ratio of the proportions of the individual compounds of formula (III) in the mixture.

[0013] Preferred compounds of formula (Ia) where x=1 are methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-butoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and phenyltri-n-butoxysilane.

[0014] More preferred are methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane, and most preferred are methyltrimethoxysilane and ethyltrimethoxysilane.

[0015] Preferred compounds of formula (Ia) where x=2 are dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-butoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-butoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-butoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and diphenyldi-n-butoxysilane.

[0016] More preferred are dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and diethyldiethoxysilane, and most preferred are dimethyldimethoxysilane and dimethyldiethoxysilane.

[0017] Preferred compounds of formula (Ia) where x=3 are trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-butoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmono-n-butoxysilane, tri-n-propylmonomethoxysilane, tri-n-propylmonoethoxysilane, tri-n-propylmono-n-butoxysilane, tri-n-butylmonomethoxysilane, tri-n-butylmonoethoxysilane, tri-n-butylmono-n-butoxysilane, triphenylmonomethoxysilane, triphenylmonoethoxysilane and triphenylmono-n-butoxysilane.

[0018] Particularly preferred are trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmonomethoxysilane and triethylmonoethoxysilane, and most preferred are trimethylmonomethoxysilane and triethylmonomethoxysilane.

[0019] In a preferred embodiment, x=1 in the use of alkoxyalkylsilanes of formula (Ia).

[0020] In a further particularly preferred embodiment, in the use of an alkoxyalkylsilane of formula (Ia), x=2, i.e. a pure dialkoxydialkylsilane is used as compound of formula (Ia).

[0021] In a further preferred embodiment, mixtures of alkoxyalkylsilanes of formula (Ia) are used, more preferably mixtures of compounds with x=2 and at least one further compound with x=1 and / or x=3, most preferably such that the compound with x=2 constitutes at least 50 mol %, in particular at least 75 mol %, especially at least 85 mol % of the mixture.

[0022] Formula (Ib) (Ib)-(-SiR 1 2-O-) y - (wherein y=3 or 4, preferably 3). It may also be possible to use cyclic siloxanes of the formula: as starting compounds.

[0023] Hexamethylcyclotrisiloxane or octamethylcyclotetrasiloxane and mixtures thereof are preferred, with hexaethylcyclotrisiloxane and octaethylcyclotetrasiloxane also being contemplated but less preferred.

[0024] Formula (III) (wherein x=2, in particular R 1 It is a preferred embodiment of the present invention when a cyclic siloxane of formula (Ib) is reacted with at least one alkoxyalkanol of formula (II) to obtain an alkoxyalkyloxysilane of formula (Ib) (wherein R is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18

[0025] Mixtures of alkoxyalkylsilanes of formula (Ia) with cyclic siloxanes of formula (Ib) are also possible, especially when the desired product consists predominantly of compounds where x=2.

[0026] In the process according to the invention, alkoxyalkylsilanes of formula (Ia) are preferred as starting compounds over cyclic siloxanes of formula (Ib).

[0027] Formula (II) (II)R 3 -O-[-CH2-CH2-O-] n -H In the at least one alkoxyalkanol, R 3 is C1-C4 alkyl, more preferably methyl, ethyl or n-butyl; and n is a positive integer of 2 to 5, preferably 2 to 4, more preferably 2 or 3, and most preferably 3.

[0028] Examples of such alkoxyalkanols, also called glycol monoalkyl ethers, are diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether and tetraethylene glycol mono-n-butyl ether.

[0029] Preferred alkoxyalkanols are diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and triethylene glycol mono-n-butyl ether.

[0030] More preferred are diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, and most preferred are triethylene glycol monomethyl ether and triethylene glycol monoethyl ether.

[0031] The alkoxyalkanols may be used alone or as mixtures, and in most cases the purified individual alkoxyalkanols will still contain small amounts of higher and lower homologous alkoxyalkanols as a result of the preparation process.

[0032] In a preferred embodiment, the proportion of alkoxyalkanols with n=3 in the total amount of alkoxyalkanols incorporated in formula (III) is at least 75% by weight, particularly preferably at least 85% by weight, very particularly preferably at least 90% and in particular at least 95% by weight.

[0033] In a further preferred embodiment, the proportion of alkoxyalkanols with n=2 in the total amount of alkoxyalkanols incorporated in formula (III) is 20% by weight or less, more preferably 10% by weight or less, most preferably 5% by weight or less. The alkoxyalkanols with n=2 may also contain small amounts of alkoxyalkanols with n=1 as a result of the preparation method. However, their content in the alkoxyalkanols with n=2 is preferably less than 7.5% by weight, more preferably less than 5% by weight, most preferably less than 2.5% by weight. Examples of such alkoxyalkanols with n=1 are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol mono-n-butyl ether.

[0034] In a further preferred embodiment, the proportion of alkoxyalkanols with n at least 4, preferably n=4, in the total amount of incorporated alkoxyalkanols in formula (III) is not more than 15% by weight, more preferably not more than 5% by weight, most preferably not more than 3% by weight. The alkoxyalkanols with n=4 may also contain small amounts of alkoxyalkanols with n>4 as a result of the preparation method. However, their content in the alkoxyalkanols with n=4 is preferably less than 5% by weight, more preferably less than 2.5% by weight, most preferably less than 1% by weight.

[0035] In formula (III), the sum of all incorporated alkoxyalkanols where n=2 to 5 is always 100% by weight.

[0036] The reaction of reactants of formula (Ia) and / or (Ib) with alkoxyalkanols of formula (II) gives compounds of formula (III) (III)R 1 x Si(-[-O-CH2-CH2-] n -OR 3 ) 4-x (In the formula, R 1 , R 3, the values ​​of n and x essentially correspond to the values ​​of the reactants used). As a result of incomplete reaction or if a mixture of alkoxyalkanols of formula (II) is used in which the individual alkoxyalkanols have different reactivities, the incorporation ratio in the product of formula (III) may deviate in each individual case from the ratio of the alkoxyalkanols of formula (II) used in the reaction.

[0037] The starting compounds of formulae (Ia) and / or (Ib) and (II) are mixed together in the desired ratio and reacted with each other.

[0038] The starting compounds can then be thoroughly mixed with one another and heated together to the desired reaction temperature. In a preferred embodiment, the starting compounds of formula (Ia) and / or (Ib) are charged first, and the alkoxyalkanol of formula (II) is added in several portions, for example 2 to 4 portions, preferably 2 or 3 portions, or continuously over the reaction time. After the addition of the alkoxyalkanol is complete, the reaction mixture is heated for a further period of time to complete the reaction.

[0039] In a further preferred embodiment, the alkoxyalkanol of formula (II) is charged initially and the starting compounds of formula (Ia) and / or (Ib) are added in several portions, for example 2 to 4 portions, preferably 2 or 3 portions, or continuously over the reaction time. After the addition of the starting compounds of formula (Ia) and / or (Ib) is complete, the reaction mixture is heated for a further period of time to complete the reaction. This embodiment is particularly preferred when the starting compounds of formula (Ia) and / or (Ib) have significant volatility under the reaction conditions and therefore escape to a significant extent from the liquid reaction mixture.

[0040] The at least one alkoxyalkanol of formula (II) is used in different molar ratios depending on the starting materials used: Use of (Ia) with x=1: The alkoxyalkanol (II) is used in a molar ratio of at least 3:1, where the molar ratio refers to the ratio of free hydroxy groups in compound (II) to silicon atoms in compound (Ia), preferably at least 3.1:1, particularly preferably at least 3.2:1 to 6:1, very particularly preferably at least 3.3:1 to 5:1, in particular at least 3.5:1 to 4:1. Use of (Ia) or (Ib) with x=2: The alkoxyalkanol (II) is used in a molar ratio of at least 2:1, where the molar ratio refers to the ratio of free hydroxy groups in compound (II) to silicon atoms in compounds (Ia) and (Ib). A ratio of at least 2.1:1 is preferred, particularly preferably at least 2.2:1 to 5:1, very particularly preferably at least 2.3:1 to 4:1, in particular at least 2.5:1 to 3:1. Use of (Ia) with x=3: The alkoxyalkanol (II) is used in a molar ratio of at least 1:1, where the molar ratio refers to the ratio of free hydroxy groups in compound (II) to silicon atoms in compound (Ia), preferably at least 1.1:1, particularly preferably at least 1.2:1 to 4:1, very particularly preferably at least 1.3:1 to 3:1, in particular at least 1.5:1 to 2:1.

[0041] Generally, the alkoxyalkanol (II) is a substituted group (R 2 O-) are used in a molar ratio of at least 1:1, preferably at least 1.1:1, particularly preferably at least 1.2:1 to 4:1, very particularly preferably at least 1.3:1 to 3:1, in particular at least 1.5:1 to 2:1.

[0042] When a mixture of compounds (Ia) having different values ​​of x is used, the alkyl groups R 1A statistical average value x' is determined, which is derived from the molar ratio of each individual compound and the value of x in each case relative to the number of alkyl groups in each individual compound. If the mixture still contains at least cyclic siloxanes of formula (Ib), their proportion per silicon atom present therein is considered as x=2.

[0043] Thus, in a mixture of compounds (Ia) containing 30 mol % when x=1, 60 mol % when x=2 and 10 mol % when x=3, for example, the alkyl group R 1 The statistical functionality of x' is 0.3×1+0.6×2+0.1×3=1.8. This means that the alkoxy group (R 2 The statistical functionality of the Si—O— or Si—O bond is (4−x′)=2.2.

[0044] In the mixture of compounds (Ia) containing 40 mol % when x=1, 40 mol % when x=2, 10 mol % when x=3 and 10 mol % hexamethylcyclotrisiloxane, the alkyl group R 1 The statistical functionality of the Si-O bond is x' = 0.4 x 1 + 0.4 x 2 + 0.1 x 3 + 0.1 x 3 x 2 = 2.1. This gives a statistical functionality of the Si-O bond of 0.4 x 3 + 0.4 x 2 + 0.1 x 1 + 0.1 x 3 x 2 = 2.7.

[0045] The alkoxyalkanol (II) is then used in at least an equimolar ratio based on the Si-O bonds, preferably at least a 1.1-fold excess, more preferably a 1.2-4-fold excess, and most preferably at least a 1.3-3-fold excess.

[0046] In a preferred embodiment of the present invention, at least one alkoxyalkanol of formula (II) is used in excess and remains in the product at the end of the reaction. In this way, mixtures of organosilicon compounds of formula (III) and at least one alkoxyalkanol of formula (II) can be obtained. These mixtures are preferably essentially composed of: 35-70% by weight of organosilicon compounds of formula (III) to 65-30% by weight of at least one alkoxyalkanol of formula (II), more preferably 40-60% by weight to 40-60% by weight, most preferably 45-55% by weight to 55-45% by weight of compounds of formula (III) to compounds of formula (II).

[0047] Residual solvents and also acid or base residues may be present in small amounts, these residues being preferably less than 5% by weight, particularly preferably less than 3% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight.

[0048] In one embodiment, the starting compounds are mixed together without the use of an additional solvent, which has the advantage that it is not necessary to remove the solvent from the reaction mixture at the end of the reaction, which is particularly preferred if the viscosity of the starting compounds and the reaction mixture under the conditions is low enough to ensure liquid transport and mixing.

[0049] In a further preferred embodiment, the reaction is carried out in at least one solvent, preferably only one solvent. The at least one solvent is preferably - open-chain or cyclic ethers, - alkanols, and - Hydrocarbons is selected from the group consisting of:

[0050] Examples of open-chain and cyclic ethers are diethyl ether, di-n-butyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tert-amyl methyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, tetrahydrofuran and dioxane.

[0051] Examples of alkanols are C1-C 10 Alkanols, preferably methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, 2-ethylhexanol, n-octanol, 2-propylheptanol and n-decanol. When an alkanol is used as the solvent, the alkanol R 2 This is the preferred embodiment when OH is used as the solvent.

[0052] Alkanols are preferred as solvents only if metal alkoxides are used as bases, in which case the preferred solvents are alkanols that are also used in the form of the metal alkoxides, otherwise the use of alkanols as solvents is less preferred.

[0053] It is preferable to use a hydrocarbon as the solvent, examples of which are aliphatic, alicyclic or aromatic C5-C 14 It mainly contains hydrocarbons.

[0054] Preferred aromatic hydrocarbons are toluene, o-, m- or p-xylene, the trimethylbenzene isomers, the tetramethylbenzene isomers, ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing such materials.

[0055] Examples of (cyclo)aliphatic hydrocarbons are decalin, alkylated decalins and isomeric mixtures of linear or branched alkanes and / or cycloalkanes, especially cyclopentane, cyclohexane, methylcyclohexane and cycloheptane.

[0056] Preferred alkanes are n-pentane, pentane isomer mixtures, n-hexane, hexane isomer mixtures, n-heptane, heptane isomer mixtures, n-octane, octane isomer mixtures, nonane isomer mixtures, n-decane and decane isomer mixtures.

[0057] Further examples of solvents include ExxonMobil Chemical's Solvesso® products, in particular Solvesso® 100 (CAS number 64742-95-6, primarily C9 and C 10 aromatics, boiling range about 154-178°C), 150 (boiling range about 182-207°C) and 200 (CAS number 64742-94-5) and Shell's Shellsol® products, Petrochem Carless' Caromax® (e.g. Caromax® 18) and DHC's Hydrosol (e.g. Hydrosol® A170, etc.). Hydrocarbon mixtures consisting of paraffins, cycloparaffins and aromatics are also commercially available as Kristalloel (for example Kristalloel 30, boiling range about 158-198°C or Kristalloel 60: CAS number 64742-82-1), white spirit (for example also CAS number 64742-82-1) or solvent naphtha (light: boiling range about 155-180°C, heavy: boiling range about 225-300°C). The aromatics content of such hydrocarbon mixtures is generally greater than 90% by weight, preferably greater than 95% by weight, more preferably greater than 98% by weight and most preferably greater than 99% by weight. It may be advantageous to use hydrocarbon mixtures with a particularly low naphthalene content.

[0058] Hydrocarbons are particularly preferred which, under the reaction conditions, act as water entrainers, especially when cyclic siloxanes of the formula (Ib) are used, or as alkanols R, especially when alkoxyalkylsilanes of the formula (Ia) are used. 2 It acts as an entrainer for OH. Preferred are hydrocarbons which form heteroazeotropes and which are distilled off from the reaction mixture and then cooled to form two phases, with the hydrocarbon phase being returned to the reaction.

[0059] The at least one solvent is particularly preferably selected from the group consisting of cyclohexane, methylcyclohexane, benzene, toluene, xylene, hexane and heptane.

[0060] When a solvent is used, the concentration of the reactants and of the at least one acid or base in the solution is generally 10% to 90% by weight, preferably 20% to 80% by weight, more preferably 30% to 70% by weight, and most preferably 40% to 60% by weight.

[0061] For example, removal of solvent by distillation results in an increase in concentration over the course of the reaction.

[0062] Although it is possible for the reaction of the starting compounds to be carried out purely thermally, the reaction in the presence of at least one acid or at least one base is preferred according to the invention.

[0063] The at least one acid is preferably - inorganic mineral acids, - organic carboxylic acids, - an organic sulfonic acid, preferably an alkyl or aryl sulfonic acid, and - Acidic ion exchanger is selected from the group consisting of:

[0064] Examples of inorganic mineral acids are hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid and phosphorous acid, of which sulfuric acid and phosphoric acid are preferred, with sulfuric acid being particularly preferred.

[0065] Among inorganic mineral acids, acids that have an oxidizing effect under reaction conditions are less preferred. It is also conceivable to select the reaction conditions of the process according to the invention so that the oxidizing effect is less pronounced, for example by lowering the reaction temperature or shortening the reaction time.

[0066] Organic carboxylic acids are C1-C 30 Carboxylic acids, preferably C2-C 20 It is preferably a monocarboxylic acid or a dicarboxylic acid, more preferably a monocarboxylic acid.

[0067] In a preferred embodiment, the carboxylic acid is a C1-C 10 The monocarboxylic acid is preferably a C2 to C6 monocarboxylic acid, and more preferably a C2 to C4 monocarboxylic acid.

[0068] In a further preferred embodiment, the carboxylic acid is 10 ~C 20 It is a fatty acid.

[0069] Specific examples of the respective organic carboxylic acids are listed below under the heading of alkali metal and alkaline earth metal carboxylates, the preferences stated there also apply to the organic carboxylic acids.

[0070] Examples of organic sulfonic acids are single to triple C6 to C6 sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, cyclododecanesulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid, and nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, or octadecylbenzenesulfonic acid. 20 -alkyl substituted benzenesulfonic acids.

[0071] Organic sulfonic acids are generally preferred over inorganic mineral acids.

[0072] Acidic ion exchangers are primarily those which have carboxylic or sulfonic acid groups, preferably carboxylic acid groups, in a polymer matrix, generally based on polystyrene, poly(meth)acrylate or poly(meth)acrylic acid. Among the acidic ion exchangers, weakly acidic ion exchangers are preferred, especially those whose acidity is determined by carboxyl groups. Very particular preference is given to those based on poly(meth)acrylic acid.

[0073] When carried out in the presence of at least one base, this is preferably an oxide or hydroxide of an alkali metal or alkaline earth metal, preferably an alkali metal hydroxide, - carbonates or hydrogen carbonates of alkali metals or alkaline earth metals, - alkali metal or alkaline earth metal hydrogen sulfates, - phosphates, hydrogen phosphates or dihydrogen phosphates of alkali metals or alkaline earth metals, - carbonates of alkali metals or alkaline earth metals, - metal alkoxide, preferably alkanol R 2 Metal alkoxides of OH, and - Amines, especially tertiary amines is selected from the group consisting of:

[0074] Examples of alkali metal or alkaline earth metal oxides and hydroxides are calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide and lithium hydroxide, of which the alkali metal hydroxides are preferred, sodium hydroxide and potassium hydroxide are particularly preferred, and sodium hydroxide is most preferred.

[0075] Examples of alkali metal or alkaline earth metal carbonates and hydrogen carbonates are calcium carbonate, magnesium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, calcium hydrogen carbonate, magnesium hydrogen carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate.

[0076] Of these, carbonates are preferred, and alkali metal carbonates are particularly preferred, with sodium carbonate, sodium bicarbonate and potassium carbonate being particularly preferred, and sodium carbonate and sodium bicarbonate being most preferred.

[0077] Examples of alkali or alkaline earth metal hydrogen sulfates are calcium hydrogen sulfate, magnesium hydrogen sulfate, lithium hydrogen sulfate, sodium hydrogen sulfate and potassium hydrogen sulfate, especially sodium hydrogen sulfate and potassium hydrogen sulfate.

[0078] Examples of alkali metal or alkaline earth metal phosphates, hydrogen phosphates or dihydrogen phosphates are calcium phosphate, magnesium phosphate, lithium phosphate, sodium phosphate, potassium phosphate, calcium hydrogen phosphate, magnesium hydrogen phosphate, lithium hydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, calcium dihydrogen phosphate, magnesium dihydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate.

[0079] Preferred examples of the alkali metal or alkaline earth metal carboxylates are C1-C 30 Carboxylic acids, preferably C2-C 20 The sodium and potassium salts of mono- or dicarboxylic acids, more preferably monocarboxylic acids.

[0080] In a preferred embodiment, the carboxylic acid is a C1-C 10 The monocarboxylic acid is preferably a C2 to C6 monocarboxylic acid, and more preferably a C2 to C4 monocarboxylic acid.

[0081] Examples of such monocarboxylic acids are acetic acid, propionic acid, n-butyric acid and isobutyric acid, pentanoic acid, pivalic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid and 2-propylheptanoic acid.

[0082] In a further preferred embodiment, the carboxylic acid is 10 ~C 20Fatty acids. Examples are decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), palmitoleic acid [(9Z)-hexadecan-9-enoic acid], oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E )-octadec-9-enoic acid], erucic acid [(13Z)-docos-13-enoic acid], linoleic acid [(9Z,12Z)-octadeca-9,12-dienoic acid], linolenic acid [(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid], eleostearic acid [(9Z,11E,13E)-octadeca-9,11,13-trienoic acid], nonadecanoic acid and arachidic acid (eicosanoic acid).

[0083] In a preferred embodiment of the present invention, a metal alkoxide is used as the base, preferably a metal C1-C4 alkoxide, more preferably a metal methoxide, ethoxide, isopropoxide, n-propoxide, n-butoxide and tert-butoxide, most preferably an alkanol R 2 A metal alkoxide of OH is used as the base.

[0084] Possible alkoxides are, less preferably, phenoxides, preferably metal salts of phenol, o-, m- or p-cresol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol, hydroquinone or hydroquinone monomethyl ether.

[0085] The metal of the metal alkoxide is preferably lithium, sodium, potassium, titanium, aluminum, zirconium, iron, cobalt, nickel and zinc, more preferably lithium, sodium, potassium, aluminum and titanium.

[0086] Sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, aluminium tri(isopropoxide), titanium tetra(n-butoxide) and titanium tetra(isopropoxide) are very particularly preferred.

[0087] Examples of tertiary amines / amines having at least one nitrogen atom with three substituents that may be used include trimethylamine, triethylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-octylamine, dimethylethanolamine, triethanolamine, N-methylmorpholine, N-methylpiperidine, N-methylpyrrolidine, pyridine, dimethylaminopyridine, dimethylaniline, 1,4-diazabicyclo[2.2.2]octane (triethylenediamine, DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0088] Preferred are tri-n-butylamine, pyridine, dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane (triethylenediamine, DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0089] The at least one acid or the at least one base is generally used in an amount of 5 to 30 mol %, preferably 10 to 25 mol %, based on the silicon atoms in the compounds (Ia) and (Ib).

[0090] The reaction temperature is between 0 (zero) and 200° C., preferably between 40 and 190° C., particularly preferably between 50 and 180° C., very particularly preferably between 60 and 170° C., in particular between 70 and 160° C. In a preferred embodiment, the reaction temperature is increased in the course of the reaction, for example by up to 80° C., preferably by up to 60° C., more preferably by up to 50° C. This is particularly preferred if the reaction proceeds to completion by increasing the temperature, with the minor components of the starting compounds being converted to an extent of at least 50%, preferably to an extent of at least 70%, more preferably to an extent of at least 80%.

[0091] It may be advantageous to carry out the reaction at superatmospheric pressure, for example at most 20, preferably at most 15, more preferably at most 10 bar superatmospheric pressure. This is particularly preferred when the boiling point of at least one of the starting compounds is about 30° C., preferably 20° C., lower than the reaction temperature.

[0092] If the boiling points of the starting compounds are sufficiently far from the desired reaction temperature, the reaction is preferably carried out at standard pressure.

[0093] To remove volatile components formed in the course of the reaction and the optionally used solvent, a negative pressure can be applied which is preferably at least 100 mbar below ambient pressure, more preferably at least 200 mbar, most preferably at least 500 mbar below ambient pressure, preferably the negative pressure is increased in the course of the reaction and removal of volatile components to a final pressure of 200 mbar, preferably 100 mbar, more preferably 50 mbar, most preferably 20 mbar.

[0094] The removed solvent, which may contain a volatile acid or base, can then be reused in subsequent runs of the reaction.

[0095] In a preferred embodiment, volatile components formed in the course of the reaction and any solvents optionally used are removed by stripping with an inert gas, preferably by passing this through the reaction mixture.

[0096] Examples of gases which are inert under the reaction conditions are nitrogen, argon, carbon dioxide or oxygen-depleted air having an oxygen content of less than 10% by volume, preferably less than 8% by volume, more preferably less than 5% by volume, preferably nitrogen or argon, more preferably nitrogen.

[0097] The inert gas may be introduced through a dip tube, ring line, nozzle or frit.

[0098] Furthermore, it may be effective to add at least one antioxidant, preferably at least one phenolic compound, to the reaction mixture. One effect of the antioxidant is to increase the yield of the reaction.

[0099] Examples of phenolic compounds are alkylphenols such as o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol or 2,2'-methylenebis(6-tert-butyl). 4,4'-oxydiphenyl, 3,4-methylenedioxydiphenol (sesamol), 3,4-dimethylphenol, hydroquinone, catechol (1,2-dihydroxybenzene), 2-(1'-methylcyclohex-1'-yl)-4,6-dimethylphenol, 2- or 4-(1'-phenyl-eth-1'-yl)-phenol, 2-tert-butyl-6-methylphenol, 2,4,6-tris-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, Tylphenol, 4-tert-butylphenol, nonylphenol [11066-49-2], octylphenol [140-66-9], 2,6-dimethylphenol, bisphenol A, bisphenol F, bisphenol B, bisphenol C, bisphenol S, 3,3',5,5'-tetrabromobisphenol A, 2,6-di-tert-butyl-p-cresol, BASFSE's Koresin®, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylcatechol, 2- Hydroxybenzyl alcohol, 2-methoxy-4-methylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4-isopropylphenol, 6-isopropyl-m-cresol, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl isocyanurate, 1,3,5-tris-(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate or pentaerythritol tetrakis[β-(3,5,-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 6-isobutyl-2,4-dinitrophenol, 6-sec-butyl-2,4-dinitrophenol, BASF SE's Irganox® 565, 1141, 1192, 1222 and 1425, octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, octyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 3-thia-1,5-pentanediol bis-[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], propionate], 4,8-dioxa-1,11-undecanediol bis-[(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate], 1,9-nonanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediamine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 1,1-methanediamine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid hydrazide, 3-(3',5'-Dimethyl-4'-hydroxyphenyl)propionic acid hydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphen-1-yl)methane, bis[3-(1'-methylcyclohex-1'-yl)-5-methyl-2-hydroxyphen-1-yl]methane, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)methane, 1 ,1-Bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)ethane, Bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)sulfide, Bis(3-tert-butyl-2-hydroxy-5-methyl-phen-1-yl)sulfide, 1,1-bis(3,4-dimethyl-2-hydroxyphen-1-yl)-2-methylpropane, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxyphen 1,3,5-tris[1'-(3'',5''-di-tert-butyl-4''-hydroxyphen-1''-yl)-meth-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5'-tert-butyl-4'-hydroxy-2'-methyl-phen-1'-yl)butane, aminophenols such as paraaminophenol, 3-diethylaminophenol, nitrosophenols such as paranitrosophenol, p-nitroso-o-cresol, alkoxyphenols such as 2-methoxyphenol (guaiacol, catechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl-4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-Dimethoxy-4-hydroxybenzyl alcohol (Syringa alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethyl vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1-(4-hydroxy-3-methoxyphenyl)ethanone (acetovanillone), eugenol, dihydroeugenol, isoeugenol, tocopherols such as α-, β-, γ-, δ- and ε-tocopherol, tocol, α-tocopherol hydroquinone and 2, 3-Dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumarin), Trolox®, gallic acid, ferulic acid, cinnamic acid and its derivatives, hydroquinone or hydroquinone monomethyl ether, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 4-methylcatechol, tert-butylhydroquinone, 3-methylcatechol, benzoquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, Methylhydroquinone, 3-methylcatechol, 4-methylcatechol, tert-butylhydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, 2,5-di-tert-butylhydroquinone, tetramethyl-p-benzoquinone, diethyl 1,4-cyclohexanedione-2,5-dicarboxylate, phenyl-p-benzoquinone, 2,5-dimethyl-3-benzyl-p-benzoquinone, 2-isopropyl-5-methyl-p-benzoquinone (thymoquinone) ), 2,6-diisopropyl-p-benzoquinone, 2,5-dimethyl-3-hydroxy-p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, embelin, tetrahydroxy-p-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2-amino-5-methyl-p-benzoquinone, 2,5-bisphenylamino-1,4-benzoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 2-anilino-1,4-naphthoquinone, anthraquinone, N,N-dimethylindoaniline, N,N-diphenyl-p-benzoquinone diimine, 1,4-benzoquinonedioxime, coellignon, 3,3'-di-tert-butyl-5,5'-dimethyldiphenoquinone, p-rosolinic acid (aurin), 2,6-di-tert-butyl-4-benzylidenebenzoquinone, 2,5-di-tert-amylhydroquinone, 3-ethyl-1,5-dimethyl-1H-pyrazol-4-ol.

[0100] When the desired conversion is reached or nearly reached, and a solvent is used, the solvent can be removed from the reaction mixture, preferably by distillation or rectification, optionally assisted by stripping with an inert gas. This can be done preferably by increasing the temperature and / or reducing the pressure of the reaction mixture, preferably by a combination of these two means. This increase in temperature usually drives the reaction to completion.

[0101] Single stage distillation may be carried out from a reactor or through suitable equipment such as a rotary evaporator, thin film evaporator, falling film evaporator, wiper blade evaporator, Sambay evaporator, and the like, and combinations thereof.

[0102] The rectification is preferably carried out via a distillation column, for example a tray column, attached to the reactor, which may be equipped with internals, valves, side draws, etc. as required. The distillation columns used may be realised in designs known per se (see, for example, Sattler, Thermische Trennverfahren [Thermal separation processes], 2nd edition 1995, Weinheim, p. 135 ff; Perry's Chemical Engineers Handbook, 7th edition 1997, New York, section 13). The distillation columns used may comprise separating internals such as separating trays, for example perforated trays, belt trays or valve trays, ordered packings, for example sheet metal or fabric packings or randomly arranged beds of random packings. A maximum of 20 theoretical separating trays, preferably a maximum of 10, are usually sufficient.

[0103] In one particular embodiment of the invention, the reaction is carried out in the form of a reactive distillation.

[0104] In this case, the reaction of the starting compounds takes place to a large extent or even completely in the separation internal parts of the separation column. The alkanol R 2 Since OH is generally the lowest boiling component in the reaction system, it is removed directly from the reaction equilibrium by distillation immediately after its formation, which allows the reaction to proceed under relatively mild conditions.The number of theoretical plates is selected in this case so that other low boiling compounds, generally the alkoxyalkylsilanes of formula (Ia) and the cyclic siloxanes of formula (Ib), remain in the reaction mixture.

[0105] In one embodiment of reactive distillation, the separation internals are coated with an acid or base in order to allow the reaction to proceed. This has the advantage that no significant reaction occurs unless the reaction mixture is in direct contact with the separation internals. This also suppresses side or further reactions that are promoted by the presence of the acid or base.

[0106] To increase contact of the reactants with the separation internals, a portion is removed from the distillation receiver and fed to the separation internals as reflux, optionally to replenish fresh unreacted alkoxyalkanol of formula (II).

[0107] In a further embodiment of the reactive distillation, at least one acid or at least one base is fed to the separation internals together with the reflux, which has the advantage that the acid or base is also present in the distillation receiver and the reaction takes place not only in the separation internals but also in the distillation receiver, which improves the space-time yield.

[0108] The at least one alkoxyalkanol of formula (II) and the product of formula (III) are generally the highest boiling components in the reaction mixture, while the reactants of formula (Ia) and / or (Ib) and the alkanol R formed are generally the highest boiling components in the reaction mixture. 2OH has a low boiling point. During the reaction, the reactants of formula (Ia) and / or (Ib) must be available for the reaction, i.e. must be maintained in the reaction mixture, while the formed alkanol R 2 OH is preferably removed from the reaction mixture. Thus, the alkanol R 2 OH is the lowest boiling compound in the system, and the boiling point of the reactants of formula (Ia) and / or (Ib) is R 2 It is a preferred embodiment when the reaction conditions and components are selected such that there is a bond between that of the OH and that of the alkoxyalkanol of formula (II) and the product of formula (III).

[0109] In this case, the reaction is carried out in a reactor equipped with a rectification column, the separation performance of which is to obtain the alkanol R 2 While ensuring that OH is sufficiently removed as a low boiler at the head of the column, R 2 It is a particularly preferred embodiment if the components in the reaction mixture that have a higher boiling point than OH, in particular the reactants of formula (Ia) and / or (Ib), are returned to the reaction mixture as column reflux. If the reaction mixture further comprises a solvent, this is preferably likewise returned to the reaction mixture as reflux or else the alkanol R 2 It may be taken as an overhead product along with OH. If the solvent and alkanol and water produced form a two-phase mixture after condensation, the solvent phase may be returned to the reaction mixture after separating the phases.

[0110] This embodiment is particularly preferred when dimethoxydimethylsilane (boiling point 81° C.) or dimethoxydiethylsilane is used as the alkoxyalkylsilane of formula (Ia), in which case methanol is released at standard pressure with a boiling point of 65° C. and can be separated or at least removed from the dimethoxydimethylsilane by rectification.

[0111] This embodiment is particularly preferred when diethoxydimethylsilane (boiling point 113-114° C.) or diethoxydiethylsilane (boiling point about 159° C.) are used as the alkoxyalkylsilane of formula (Ia). In this case, ethanol is released at a boiling point of 78° C. at standard pressure and can be separated or at least removed from dimethoxydimethylsilane and diethoxydiethylsilane by rectification.

[0112] This embodiment is particularly preferred when the cyclic siloxane of formula (Ib) used is hexamethylcyclotrisiloxane (boiling point 134° C.) or octamethylcyclotetrasiloxane (boiling point 175-176° C.). In this case, water is released at boiling point 100° C. at standard pressure and can be separated or at least removed by rectification.

[0113] At the end of the reaction, the unreacted reactants of formula (Ia) and / or (Ib) and any solvent present are then removed from the reaction mixture by distillation.

[0114] After removing the solvent, the reaction mixture is purified.

[0115] When the desired conversion has been achieved, and no solvent was used, the reaction is typically stopped by cooling and the reaction mixture is purified by leaving the reaction mixture at a temperature at which it has a sufficiently low viscosity for purification.

[0116] Purification may involve removing at least one acid or base and any solvent still present at the end of the reaction. - Filtration, - membrane filtration, - reverse osmosis, - adsorption onto at least one inorganic metal oxide or activated carbon; and - contact with at least one acidic, basic or mixed ion exchanger The oxidized or unoxidized substances are removed through at least one purification step selected from the group consisting of:

[0117] The first three techniques are well known to those skilled in the art.

[0118] Adsorption can be carried out on inorganic materials such as silica gels, silicates, aluminas, zeolites, diatomaceous earth, mixed aluminium / silicon oxides and also calcium carbonates and oxides or activated carbon or charcoal.

[0119] The basic material is preferably used to remove the acid, and vice versa.

[0120] The acid is preferably removed by passing the reaction mixture through a basic ion exchanger and the base is removed by passing the reaction mixture through an acidic ion exchanger.

[0121] Once purified, the reaction mixture is essentially free of acids, bases and solvents and can be used as or in functional fluids, preferably hydraulic or brake fluids, and to scavenge water.

[0122] Due to the intended use it may be necessary to add further typical additives to the reaction mixture, examples being corrosion inhibitors, antifoam agents, pH stabilizers or antioxidants.

[0123] The advantage of the described method of the present invention is that the reaction mixture can be obtained under mild conditions.In particular, the reaction mixture does not contain halides, especially chlorides, which means that the reaction mixture shows lower corrosivity than the corresponding compound obtained from the corresponding alkylchlorosilane.The content of halides, especially chlorides, in the reaction mixture thus obtained is generally less than 100 ppm by weight, preferably less than 75 ppm, particularly preferably less than 50 ppm, very preferably less than 25 ppm, particularly less than 15 ppm, even less than 10 ppm. EXAMPLES

[0124] General Procedure (Example 1) To a three-neck flask equipped with a water separator, reflux condenser, thermometer, and nitrogen inlet was added 40 ml of cyclohexane, followed by triethylene glycol monomethyl ether (50.0 g, 0.30 mol, 2.0 equiv.), dimethoxydimethylsilane (18.3 g, 0.15 mol, 1.0 equiv.), and sodium methoxide (0.40 g, 7.5 mmol, 5 mol %).

[0125] The mixture was stirred at room temperature for 5 min and then heated to reflux for 6.5 h. After cooling to room temperature, the crude product was purified by vacuum distillation (22-160° C., 0.24 mbar).

[0126] The product fraction (21.0 g, 57 mmol, 37% isolated yield) passed as a colorless liquid at 142° C. and 0.24 mbar. The structure was confirmed by NMR and high resolution mass spectrometry (HRMS).

[0127] HRMS: expected value 402.2518 [M+NH4] + , measured value 402.2514 1 H NMR (500MHz, CDCl3): δ=0.02(s,6H),3.25(s,6H)3.42(m,4H),3.46(t,J=5.3Hz,4H),3.50-3.60(m,12H),3.71(t,J=5.3Hz,4H). 13 C NMR(125MHz,CDCl3):δ=-3.5,55.6,61.4,70.1,70.20.70.23,71.5,72.0, 29 Si NMR (99 MHz, CDCl3): δ = -1.85.

[0128] Example 2 - Varying the starting material As in Example 1, the starting materials specified in the table were reacted with triethylene glycol monomethyl ether (MTG-OH) in a 2:1 molar ratio at the temperature specified for the time stated.

[0129] The yield in the reaction mixture is calculated assuming that only the product and unreacted triethylene glycol monomethyl ether are present in the reaction mixture. 1 Determined by 1 H NMR.

[0130] [Table 1]

[0131] Example 3 - Changing the catalyst As in Example 1, diethoxydimethylsilane was reacted with 2.0 equivalents of triethylene glycol monomethyl ether in the presence of the catalyst specified in the table in the amount specified at 126° C. for the time indicated.

[0132] As in Example 2, the yield in the reaction mixture was: 1 Determined by 1 H NMR.

[0133] [Table 2]

[0134] Example 4 - Modification of alkoxyalkanol As in Example 1, diethoxydimethylsilane was reacted with 2.0 equivalents of the indicated alkoxyalkanol in the presence of 5 mol % sodium ethoxide at 135° C. for 2.5 hours, followed by application of a vacuum of 100 mbar for an additional hour.

[0135] Yields refer to isolated yields and purity was determined by NMR.

[0136] [Table 3]

[0137] Higher alkoxyalkanols where n=2 and n=3 have been found to give higher yields in the reaction than monoethylene glycol monomethyl ether.

[0138] Example 5 - Varying the amount of catalyst and the amount of alkoxyalkanol Similar to Example 1, diethoxydimethylsilane was reacted with the indicated equivalents of triethylene glycol monomethyl ether (MTG-OH) in the presence of 1 mole % sodium bicarbonate (NaHCO) at 126° C. for the times indicated.

[0139] In some experiments, 1000 ppm of antioxidant (dissolved in triethylene glycol monomethyl ether) was further added to the reaction mixture according to the table. As in Example 2, the yield in the reaction mixture was: 1 Determined by H-NMR.

[0140] [Table 4]

[0141] It can be seen that the addition of an antioxidant significantly increases the yield.

Claims

1. Formula (III) (III) R １ ｘ Si (-[-O-CH ２ --H ２ -] ｎ -O-R ３ ) ４－ｘ 1. A method for preparing an organosilicon compound or mixture thereof of formula (Ia): (Ia)R １ ｘ Si(OR ２ ) ４－ｘ and / or at least one alkoxyalkylsilane of formula (Ib) (Ib)-(-SiR １ ２ - O - ｙ - The cyclic siloxane of formula (II) (II)R ３ -O-[-CH ２ -CH ２ -O-] ｎ -H in the presence of at least one acid or at least one base, optionally in a solvent, at a temperature of 0 to 200° C., wherein R １ is phenyl or C １ ~C ４ Alkyl, preferably C １ ~C ４ alkyl, more preferably methyl, ethyl or n-butyl, most preferably methyl or ethyl; R ２ is C １ ~C ４ alkyl, more preferably methyl, ethyl or n-butyl, most preferably methyl or ethyl; R ３ is C １ ~C ４ alkyl, more preferably methyl, ethyl or n-butyl; x is a positive integer 1, 2, or 3; y is a positive integer 3 or 4, preferably 3, and The method wherein n is a positive integer from 2 to 5, preferably from 2 to 4, more preferably 2 or 3, and most preferably 3.

2. 2. The method of claim 1, wherein only compounds in which x=2 are used as the alkoxyalkylsilane of formula (Ia).

3. The at least one alkoxyalkanol of formula (II) is a substituted group (R ２ 2. The process according to claim 1, wherein the hydroxybenzoates are used in a molar ratio of at least 1:1, preferably at least 1.1:1, particularly preferably at least 1.2:1 to 4:1, very particularly preferably at least 1.3:1 to 3:1, in particular at least 1.5:1 to 2:1 per hydroxybenzoate (O-).

4. The at least one solvent is open-chain or cyclic ethers, - alkanols, and - Hydrocarbons 2. The method of claim 1, wherein the compound is selected from the group consisting of:

5. The solvent is Alkanol R ２ 5. The method of claim 4, wherein the hydroxy group is OH.

6. The solvent is water and / or alkanol R under the reaction conditions. ２ 5. The method of claim 4, wherein the hydrocarbon acts as an entrainer for OH.

7. 7. The method of claim 6, wherein the hydrocarbon is cyclohexane, methylcyclohexane, benzene, toluene, xylene, hexane, or heptane.

8. The reaction is alkali metal or alkaline earth metal oxides or hydroxides, preferably alkali metal hydroxides, - carbonates or hydrogen carbonates of alkali metals or alkaline earth metals, - alkali metal or alkaline earth metal hydrogen sulfates, - phosphates, hydrogen phosphates or dihydrogen phosphates of alkali metals or alkaline earth metals, - carbonates of alkali metals or alkaline earth metals, metal alkoxides, preferably the alkanols R ２ metal alkoxides of OH, and - amine 10. The method of claim 1, wherein the method is carried out in the presence of at least one base selected from the group consisting of:

9. The reaction is an inorganic mineral acid, preferably sulfuric acid, organic carboxylic acids, organic sulfonic acids, preferably alkyl or aryl sulfonic acids, and - Acidic ion exchanger 10. The process of claim 1, wherein the process is carried out in the presence of at least one acid selected from the group consisting of:

10. 2. The method according to claim 1, wherein volatile components formed during the course of the reaction and optionally the solvent are removed by applying a negative pressure of at least 100 mbar below ambient pressure, preferably the negative pressure being increased during the course of the reaction.

11. 2. The process according to claim 1, wherein the volatile components formed in the course of the reaction and the solvent optionally used are removed by stripping with an inert gas, preferably by passing it through the reaction mixture.

12. The reaction is carried out in a reactor equipped with a rectification column, the separation performance of which is ２ Ensure that OH is sufficiently removed as a low boiler at the column head, and that alkanol R ２ 2. The method of claim 1, wherein components in the reaction mixture that have a boiling point higher than OH, in particular the reactants of formula (Ia) and / or (Ib), are returned to the reaction mixture as column reflux.

13. 13. The method of claim 12, wherein the alkoxyalkylsilane of formula (Ia) is selected from the group consisting of dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, and diethoxydiethylsilane.

14. 10. The method of claim 1, wherein the at least one alkoxyalkanol of formula (II) is introduced into the reaction in portions or continuously over the course of the reaction.

15. 2. The method of claim 1, wherein the starting compound of formula (Ia) and / or (Ib) is introduced into the initially charged alkoxyalkanol of formula (II) in portions or continuously over the course of the reaction.

16. The method of claim 1 , wherein the reaction temperature is increased during the course of the reaction.

17. The at least one acid or base, at the end of the reaction, - filtration, - membrane filtration, - reverse osmosis, - adsorption onto at least one inorganic metal oxide or activated carbon, and - contact with at least one acidic, basic or mixed ion exchanger 2. The method of claim 1, wherein the hydroxybenzoates are removed through at least one purification step selected from the group consisting of:

18. 10. The method of claim 1, wherein an excess of the at least one alkoxyalkanol of formula (II) is essentially left in the reaction mixture.

19. 10. Use of the reaction mixture obtained by the process according to claim 1 as or in a functional fluid, preferably a hydraulic or brake fluid, and for capturing water.