RU2391291C2 - Method of obtaining organosilanes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention can be used to obtain organosilanes by reacting (haloorganyl)alkoxysilane with a sulphonating agent. The reagent is selected from hydroxysulphides of alkali metals, sulphides of alkali metals Me₂S, polysulphides of alkali metals Me₂S_g and any combinations, where Me denotes an alkali metal, NH₄ or (alkali-earth metal)_1/2, and g ranges from 1.5 to 8.0. The reaction is also optionally carried out with sulphur and/or H₂S in alcohol. Me₂S or Me₂S_g contains more than 10 wt % water and the alkali metal hydrosulphide contains more than 3 wt % water.

EFFECT: invention enables use of water-containing sulphonating agents and shortening the reaction time for obtaining organosilanes.

8 cl, 21 ex

Description

The invention relates to a method for producing organosilanes.

GB 1102251 describes the reaction of anhydrous alkali metal hydrosulfides with (haloalkyl) alkoxysilanes in a methanol medium under atmospheric pressure to produce the corresponding (mercaptoalkyl) alkoxysilanes. The disadvantages of this method are an unusually long reaction time (96 hours) to achieve a high degree of conversion and an unsatisfactory yield.

It is known that (mercaptoalkyl) alkoxysilanes can be prepared by reacting an anhydrous alkali metal hydrosulfide with acceptable (haloalkyl) alkoxysilanes in the presence of a 10 to 100% molar excess of H ₂ S (US 5,840,952). Before adding (haloalkyl) alkoxysilane in a preferred embodiment, an alkali metal hydrosulfide is prepared by reacting an alkali metal sulfide Me ₂ S (Me is Li, Na, K) with H ₂ S or by reacting an H ₂ S with an alkali metal alcoholate. When implemented on an industrial scale, this method is characterized by the disadvantage that it requires storage, dosing and various manipulations with highly toxic H ₂ S and the method is carried out in 2 stages, as a result of which the volumetric productivity of the process is reduced in principle.

In addition, it is known that (mercaptoalkyl) alkoxysilanes can be prepared by reacting (haloalkyl) alkoxysilanes with anhydrous alkali metal hydrosulfide (NaSH) in polar aprotic solvents (EP 0471164). The disadvantage of this method is that it uses large amounts of solvent, at least 50 vol.%, And it can be toxic, for example in the case of dimethylformamide. In addition, the high boiling point of dimethylformamide complicates the subsequent distillation processing of the reaction products.

DE 10351735 describes a process for the preparation of (mercaptoorganyl) alkoxysilanes, wherein anhydrous dried alkali metal hydrosulfide is reacted with a mixture of (haloorgan) alkoxysilane and (haloorgan) halosilanes in alcohol in a closed vessel in the absence of air and under elevated pressure. The disadvantage of this method is the use of anhydrous alkali metal hydrosulfide.

EP 1130023 describes the preparation of organosilylalkyl polysulfanes of the general formula

(R ¹ R ² R ³ Si-R ⁴ -) ₂ S _q

from organosilylalkyl halide of the general formula

R ¹ R ² R ³ Si-R ⁴ -X.

This reaction is first carried out by introducing elemental sulfur and an alkyl alkyl halide into a polar organic solvent and adding an anhydrous or substantially anhydrous ionic sulfide to the suspension. Due to the sensitivity of the Si alkoxy bonds of the organosilylalkyl halide to hydrolysis, the ionic sulfides must be anhydrous or practically anhydrous.

The aim of the present invention is to develop a method for producing organosilanes, the implementation of which allows to reduce the reaction time in combination with a good yield of crude product and in which you can use water-containing sulfonating reagents.

The object of the invention is a method for producing organosilanes of the general formula I

wherein

R are the same or different and represent a C ₁ -C ₈ alkyl group, preferably CH ₃ or CH ₂ CH ₃ , C ₁ -C ₈ alkenyl, C ₁ -C ₈ aryl or C ₁ -C ₈ aralkyl group or OR 'group,

R 'are the same or different and represent a branched or straight chain monovalent C ₁ -C ₂₄ -, preferably C ₁ -C ₄ - or C ₁₂ -C ₁₈ -, alkyl or alkenyl group, particularly preferably CH ₂ CH ₃ , aryl group, aralkyl a group, a hydrogen atom (-H), an aliphatic ether group O- (CR ^III ₂ ) -O-Alk or O- (CR ^III ₂ ) _y -O-Alk, or an aliphatic simple polyether group O- (CR ^III ₂ O ) _y -Alk, or O- (CR ^III ₂ -CR ^III ₂ -O) _y -Alk, where y is from 2 to 20, preferably from 2 to 10, particularly preferably from 3 to 6, R ^III independently of each other denote H or lkilnuyu group, preferably a CH ₃ group, a Alk represents a branched or straight chain saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic monovalent C ₁ -C ₃₀ -, preferably C ₂ -C ₂₀ -; particularly preferably C ₆ -C ₁₈ -, even more preferably C ₁₀ -C ₁₈ -, a hydrocarbon group, R ″ is a branched or straight chain saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C ₁ -C ₃₀ -, preferably C ₁ -C ₂₀ -, particularly preferably C ₁ -C ₁₀ -, even more preferably C ₁ -C ₇ -, a hydrocarbon group which is optionally substituted with F, Cl, Br, I, HS, NH ₂ or NHR ', X is S if n is 2, am is a sulfur chain of average length from 1.5 to 4.5, and X is SH if n is chaet 1 and m is 1, by reacting (galoorganil) alkoxysilane of the formula II

in which R, R 'and R "have the above meanings, a Hal represents an atom of chlorine, bromine, fluorine or iodine,

with a sulfonating reagent selected from the group consisting of alkali metal hydrosulfide, Me ₂ S metal sulfide, Me ₂ S _g metal polysulfide and any target combination thereof, where Me is an alkali metal, NH ₄ or (alkaline earth metal) _1/2 , ag is from 1.5 to 8.0, and optionally additionally with sulfur and / or H ₂ S in alcohol, which is characterized in that Me ₂ S or Me ₂ S _g contains more than 10, preferably more than 15, particularly preferably more than 20, even more preferably more than 30 wt.% water, and the alkali metal hydrosulfide contains more than 3, p preferably more than 5, particularly preferably more than 10, even more preferably more than 12, most preferably more than 15 wt.% water.

It was found that the water contained in sulfonating reagents does not cause complete hydrolysis and condensation of alkoxysilanes, although there are basic reaction conditions and stoichiometrically contains more water than is required to convert all available SiOR bonds to SiOH, and subsequently the condensation reaction into the corresponding siloxanes containing Si-O-Si bonds.

R ″ may be —CH ₂ -, —C ₂ CH ₂ -, —CH ₂ CH ₂ CH ₂ -, —CH ₂ CH ₂ CH ₂ CH ₂ -, —CH (CH ₃ ) -,

—CH ₂ CH (CH ₃ ) -, —CH (CH ₃ ) CH ₂ -, —C (CH ₃ ) ₂ -, —CH (C ₂ H ₅ ) -, —CH ₂ CH ₂ CH (CH ₃ ) - , -CH ₂ CH (CH ₃ ) CH ₂ - or a group

The sulfonating reagent and optionally sulfur and / or H ₂ S may be alkali metal hydrosulfide, Me ₂ S, Me ₂ S _g , alkali metal hydrosulfide + sulfur, Me ₂ S + sulfur, Me ₂ S _g + sulfur, alkali metal hydrosulfide + Me ₂ S _g + Me ₂ S, Me ₂ S _g + Me ₂ S, alkali metal hydrosulfide + Me ₂ S + sulfur, alkali metal hydrosulfide + Me ₂ S _g + sulfur, Me ₂ S + Me ₂ S _g + sulfur, alkali metal hydrosulfide + Me ₂ S _g + Me ₂ S + sulfur, H ₂ S + Me ₂ S _g + Me ₂ S + sulfur, H ₂ S + alkali metal hydrosulfide + Me ₂ S _g + Me ₂ S + sulfur, H ₂ S + alkali metal hydrosulfide + Me ₂ S _g + Me ₂ S, H ₂ S + alkali hydrosulfide IU alla + Me ₂ S, H ₂ S + hydrosulphide of alkaline metal + Me ₂ S _g, H ₂ S + Me ₂ S + sulfur, H ₂ S + Me ₂ S _g + sulfur, H ₂ S + Me ₂ S _g + Me ₂ S, H ₂ S + Me ₂ S _g or H ₂ S + Me ₂ S.

As the alkali metal hydrosulfide, lithium hydrosulfide (LiSH), sodium hydrosulfide (NaSH), potassium hydrosulfide (KSH) and cesium hydrosulfide (CsSH) can be used.

As the alkali metal sulfide Me ₂ S or the polysulfide of the alkali metal Me ₂ S _g , Li ₂ S, Na ₂ S, K ₂ S, Na ₂ S ₂ , Na ₂ S ₃ , Na ₂ S ₄ , K ₂ S _{2 can be used} , K ₂ S ₃ , K ₂ S ₄ or mixtures thereof.

Anhydrous sulfonating reagents may include less than 60, preferably less than 50, particularly preferably less than 40, even more preferably less than 35 wt.% Water.

Anhydrous sulfonating agents may include in the range of 10 to 60, preferably in the range of 10 to 50, particularly preferably in the range of 15 to 50% by weight of water.

The water content in the sulfonating reagents is set as follows: to determine the water content by exhaled air, the glass balls fog up, they are coated with phosphorus pentoxide, and then placed in a U-shaped tube. About 3 g of sample is weighed into a 50 ml flask, incubated for 2 hours at 320 ° C in a stream of nitrogen (30 ml / min), dried with Sicapent, and then allowed to stand for a further 30 minutes in a stream of nitrogen. A wet gaseous carrier is passed from the flask into the U-tube by means of a connecting tube. During the heating phase, the use of a hot air blower eliminates the possibility of condensation between the bulb and the U-tube. The U-shaped tube is again weighed and the amount of water released from the sulfonating reagents is determined gravimetrically.

Upon receipt of organosilanes in the method in accordance with the invention, compounds of the general formula I or mixtures of compounds of the general formula I can be formed.

The compounds of general formula I that are formed in the method according to the invention or mixtures of compounds of general formula I may have a water content of less than 3, preferably less than 2, particularly preferably less than 1, even more preferably less than 0.5 wt.%, As determined in accordance with DIN ENISO 12937, including iodometric back titration to clearly distinguish between H ₂ O and HS materials (H ₂ S, etc.).

The aliphatic polyether group in formulas I and II may include ethylene oxide (CH ₂ —CH ₂ —O) and propylene oxide units, for example (CH (CH ₃ ) —CH ₂ —O) or (CH ₂ —CH (CH ₃ ) —O )

The aliphatic polyether group O- (CR ^III ₂ O) _y -Alk or O- (CR ^III ₂ -CR ^III ₂ O) _y -Alk may be

O- (CH ₂ —CH ₂ O) ₂ —C ₈ H ₁₇ , O- (CH ₂ —CH ₂ O) ₃ —C ₈ H ₁₇ , O- (CH ₂ -CH ₂ O) ₄ -C ₈ H ₁₇ , O- (CH ₂ -CH ₂ O) ₅ -C ₈ H ₁₇ , O- (CH ₂ —CH ₂ O) ₆ —C ₈ H ₁₇ , O- (CH ₂ -CH ₂ O) ₇ -C ₈ H ₁₇ , O- (CH (CH ₃ ) -CH ₂ O) ₂ -C ₈ H ₁₇ , O- (CH (CH ₃ ) —CH ₂ O) ₃ —C ₈ H ₁₇ , O- (CH (CH ₃ ) -CH ₂ O) ₄ -C ₈ H ₁₇ , O- (CH (CH ₃ ) -CH ₂ O) ₅ -C ₈ H ₁₇ , O- (CH (CH ₃ ) -CH ₂ O) ₆ -C ₈ H ₁₇ , O- (CH (CH ₃ ) -CH ₂ O) ₇ -C ₈ H ₁₇ , O- (CH ₂ -CH ₂ O) ₂ -C ₉ H ₁₉ , O- (CH ₂ -CH ₂ O) ₃ -C ₉ H ₁₉ , O- (CH ₂ -CH ₂ O) ₄ -C ₉ H ₁₉ , O- (CH ₂ —CH ₂ O) ₅ —C ₉ H ₁₉ , O- (CH ₂ -CH ₂ O) ₆ -C ₉ H ₁₉ , O- (CH ₂ —CH ₂ O) ₇ —C ₉ H ₁₉ , O- (CH (CH ₃ ) —CH ₂ O) ₂ —C ₉ H ₁₉ , O- (CH (CH ₃ ) —CH ₂ O) ₃ —C ₉ H ₁₉ , O- (CH (CH ₃ ) —CH ₂ O) ₄ —C ₉ H ₁₉ , O- (CH (CH ₃ ) —CH ₂ O) ₅ —C ₉ H ₁₉ , O- (CH (CH ₃ ) —CH ₂ O) ₆ —C ₉ H ₁₉ , O- (CH (CH ₃ ) —CH ₂ O) ₇ —C ₉ H ₁₉ , O- (CH ₂ —CH ₂ O) ₂ —C ₁₀ H ₂₁ , O- (CH ₂ -CH ₂ O) ₃ -C ₁₀ H ₂₁ , O- (CH ₂ -CH ₂ O) ₄ -C ₁₀ H ₂₁ , O- (CH ₂ -CH ₂ O) ₅ -C ₁₀ H ₂₁ , O- (CH ₂ -CH ₂ O) ₆ -C ₁₀ H ₂₁ , O- (CH ₂ -CH ₂ O) ₇ -C ₁₀ H ₂₁ , O- (CH (CH ₃ ) -CH ₂ O) ₂ -C ₁₀ H ₂₁ , O- (CH (CH ₃ ) -CH ₂ O) ₃ -C ₁₀ H ₂₁ , O- (CH (CH ₃ ) -CH ₂ O) ₄ -C ₁₀ H ₂₁ , O- (CH (CH ₃ ) -CH ₂ O) ₅ -C ₁₀ H ₂₁ , O- (CH (CH ₃ ) -CH ₂ O) ₆ -C ₁₀ H ₂₁ , O- (CH (CH ₃ ) -CH ₂ O) ₇ -C ₁₀ H ₂₁ , O- (CH ₂ —CH ₂ O) ₂ —C ₁₁ H ₂₃ , O- (CH ₂ -CH ₂ O) ₃ -C ₁₁ H ₂₃ , O- (CH ₂ -CH ₂ O) ₄ -C ₁₁ H ₂₃ , O- (CH ₂ -CH ₂ O) ₅ -C ₁₁ H ₂₃ , O- (CH ₂ -CH ₂ O) ₆ -C ₁₁ H ₂₃ , O- (CH ₂ -CH ₂ O) ₇ -C ₁₁ H ₂₃ , O- (CH (CH ₃ ) —CH ₂ O) ₂ —C ₁₁ H ₂₃ , O- (CH (CH ₃ ) -CH ₂ O) ₃ -C ₁₁ H ₂₃ , O- (CH (CH ₃ ) -CH ₂ O) ₄ -C ₁₁ H ₂₃ , O- (CH (CH ₃ ) -CH ₂ O) ₅ -C ₁₁ H ₂₃ , O- (CH (CH ₃ ) -CH ₂ O) ₆ -C ₁₁ H ₂₃ , O- (CH (CH ₃ ) -CH ₂ O) ₇ -C ₁₁ H ₂₃ , O- (CH ₂ -CH ₂ O) ₂ -C ₁₂ H ₂₅ , O- (CH ₂ -CH ₂ O) ₃ -C ₁₂ H ₂₅ , O- (CH ₂ -CH ₂ O) ₄ -C ₁₂ H ₂₅ , O- (CH ₂ -CH ₂ O) ₅ -C ₁₂ H ₂₅ , O- (CH ₂ -CH ₂ O) ₆ -C ₁₂ H ₂₅ , O- (CH ₂ -CH ₂ O) ₇ -C ₁₂ H ₂₅ , O- (CH (CH ₃ ) -CH ₂ O) ₂ -C ₁₂ H ₂₅ , O- (CH (CH ₃ ) -CH ₂ O) ₃ -C ₁₂ H ₂₅ , O- (CH (CH ₃ ) -CH ₂ O) ₄ -C ₁₂ H ₂₅ , O- (CH (CH ₃ ) -CH ₂ O) ₅ -C ₁₂ H ₂₅ , O- (CH (CH ₃ ) -CH ₂ O) ₆ -C ₁₂ H ₂₅ , O- (CH (CH ₃ ) -CH ₂ O) ₇ -C ₁₂ H ₂₅ , O- (CH ₂ —CH ₂ O) ₂ —C ₁₃ H ₂₇ , O- (CH ₂ -CH ₂ O) ₃ -C ₁₃ H ₂₇ , O- (CH ₂ -CH ₂ O) ₄ -C ₁₃ H ₂₇ , O- (CH ₂ —CH ₂ O) ₅ —C ₁₃ H ₂₇ , O- (CH ₂ -CH ₂ O) ₆ -C ₁₃ H ₂₇ , O- (CH ₂ -CH ₂ O) ₇ -C ₁₃ H ₂₇ , O- (CH (CH ₃ ) —CH ₂ O) ₂ —C ₁₃ H ₂₇ , O- (CH (CH ₃ ) —CH ₂ O) ₃ —C ₁₃ H ₂₇ , O- (CH (CH ₃ ) -CH ₂ O) ₄ -C ₁₃ H ₂₇ , O- (CH (CH ₃ ) -CH ₂ O) ₅ -C ₁₃ H ₂₇ , O- (CH (CH ₃ ) -CH ₂ O) ₆ -C ₁₃ H ₂₇ , O- (CH (CH ₃ ) -CH ₂ O) ₇ -C ₁₃ H ₂₇ , O- (CH ₂ —CH ₂ O) ₂ —C ₁₄ H ₂₉ , O- (CH ₂ -CH ₂ O) ₃ -C ₁₄ H ₂₉ , O- (CH ₂ -CH ₂ O) ₄ -C ₁₄ H ₂₉ , O- (CH ₂ -CH ₂ O) ₅ -C ₁₄ H ₂₉ , O- (CH ₂ -CH ₂ O) ₆ -C ₁₄ H ₂₉ , O- (CH ₂ -CH ₂ O) ₇ -C ₁₄ H ₂₉ , O- (CH (CH ₃ ) —CH ₂ O) ₂ —C ₁₄ H ₂₉ , O- (CH (CH ₃ ) —CH ₂ O) ₃ —C ₁₄ H ₂₉ , O- (CH (CH ₃ ) -CH ₂ O) ₄ -C ₁₄ H ₂₉ , O- (CH (CH ₃ ) -CH ₂ O) ₅ -C ₁₄ H ₂₉ , O- (CH (CH ₃ ) -CH ₂ O) ₆ -C ₁₄ H ₂₉ , O- (CH (CH ₃ ) -CH ₂ O) ₇ -C ₁₄ H ₂₉ , O- (CH ₂ -CH ₂ O) ₂ -C ₁₅ H ₃₁ , O- (CH ₂ -CH ₂ O) ₃ -C ₁₅ H ₃₁ , O- (CH ₂ -CH ₂ O) ₄ -C ₁₅ H ₃₁ , O- (CH ₂ -CH ₂ O) ₅ -C ₁₅ H ₃₁ , O- (CH ₂ -CH ₂ O) ₆ -C ₁₅ H ₃₁ , O- (CH ₂ -CH ₂ O) ₇ -C ₁₅ H ₃₁ , O- (CH (CH ₃ ) —CH ₂ O) ₂ —C ₁₅ H ₃₁ , O- (CH (CH ₃ ) -CH ₂ O) ₃ -C ₁₅ H ₃₁ , O- (CH (CH ₃ ) -CH ₂ O) ₄ -C ₁₅ H ₃₁ , O- (CH (CH ₃ ) -CH ₂ O) ₅ -C ₁₅ H ₃₁ , O- (CH (CH ₃ ) -CH ₂ O) ₆ -C ₁₅ H ₃₁ , O- (CH (CH ₃ ) -CH ₂ O) ₇ -C ₁₅ H ₃₁ , O- (CH ₂ —CH ₂ O) ₂ —C ₁₆ H ₃₃ , O- (CH ₂ —CH ₂ O) ₃ —C ₁₆ H ₃₃ , O- (CH ₂ —CH ₂ O) ₄ —C ₁₆ H ₃₃ , O- (CH ₂ —CH ₂ O) ₅ —C ₁₆ H ₃₃ , O- (CH ₂ —CH ₂ O) ₆ —C ₁₆ H ₃₃ , O- (CH ₂ —CH ₂ O) ₇ —C ₁₆ H ₃₃ , O- (CH (CH ₃ ) —CH ₂ O) ₂ —C ₁₆ H ₃₃ , O- (CH (CH ₃ ) —CH ₂ O) ₃ —C ₁₆ H ₃₃ , O- (CH (CH ₃ ) —CH ₂ O) ₄ —C ₁₆ H ₃₃ , O- (CH (CH ₃ ) —CH ₂ O) ₅ —C ₁₆ H ₃₃ ,

O- (CH (CH ₃ ) -CH ₂ O) ₆ -C ₁₆ H ₃₃ or O- (CH (CH ₃ ) -CH ₂ O) ₇ -C ₁₆ H ₃₃ .

(Haloorganyl) alkoxysilanes of the formula II, which may be used in a preferred embodiment, are

3-chlorobutyl (triethoxysilane),

3-chlorobutyl (trimethoxysilane),

3-chlorobutyl (diethoxymethoxysilane),

3-chloropropyl (triethoxysilane),

3-chloropropyl (trimethoxysilane),

3-chloropropyl (diethoxymethoxysilane),

2-chloroethyl (triethoxysilane),

2-chloroethyl (trimethoxysilane),

2-chloroethyl (diethoxymethoxysilane),

1-chloromethyl (triethoxysilane),

1-chloromethyl (trimethoxysilane),

1-chloromethyl (diethoxymethoxysilane),

3-chloropropyl (diethoxymethylsilane),

3-chloropropyl (dimethoxymethylsilane),

2-chloroethyl (diethoxymethylsilane),

2-chloroethyl (dimethoxymethylsilane),

1-chloromethyl (diethoxymethylsilane),

1-chloromethyl (dimethoxymethylsilane),

3-chloropropyl (ethoxydimethylsilane),

3-chloropropyl (methoxydimethylsilane),

2-chloroethyl (ethoxydimethylsilane),

2-chloroethyl (methoxydimethylsilane),

1-chloromethyl (ethoxydimethylsilane),

1-chloromethyl (methoxydimethylsilane),

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₆ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] (MeO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (MeO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₆ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] (EtO) ₂ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (EtO) Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₉ H ₁₉ E- (CH ₂ -CH ₂ O) ₆ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] ₃ Si (CH ₂ ) ₃ Cl,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] ₃ Si (CH ₂ ) ₃ Cl and

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] ₃ Si (CH ₂ ) ₃ Cl.

The (haloorganyl) alkoxysilane may be a (haloorganyl) alkoxysilane of formula II or a mixture of (haloorganyl) alkoxysilanes of formula II.

Additives may be administered before, during, or after the reaction.

Additives may be non-alcohol solvents. In a preferred embodiment, alkanes, such as, for example, pentane, hexane, cyclohexane, heptane and octane, an ether, such as, for example, diethyl ether, tetrahydrofuran, can be used as additives, which are non-alcohol solvents, in pure form or in technical grade. , 1,2-dimethoxyethane, dioxane, dioxolane, ethylene glycols and propylene glycols, aromatic solvents such as, for example, benzene, toluene, o-xylene, m-xylene and p-xylene or carbonyl-containing solvents, such as, for example, dimethylformamide.

At the beginning of the reaction and / or during the reaction and / or at the end of the reaction, polar protic, aprotic basic or acidic additives can be added to the reaction mixture.

Additives can be, for example, H ₂ S (alkali metal ion) H ₂ PO ₄ , (alkali metal ion) ₂ HPO ₄ , (alkali metal ion) ₃ PO ₄ , (alkali metal ion) HCO ₃ , (alkali metal ion) ₂ CO ₃ , (alkali metal ion) ₂ SO ₄ and (alkali metal ion) HSO ₄ . In a preferred embodiment, KH ₂ PO ₄ , K ₂ HPO ₄ , KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ or Na ₂ CO ₃ can be used.

The crude product yield of the process according to the invention may be greater than 80, preferably greater than 85, particularly preferably greater than 90, even more preferably greater than 95%, based on the theoretical yield, taking into account the amount of (haloorganyl) alkoxysilane used.

The yield of crude product can be a gravimetric determination of the totality of all liquid compounds isolated after removal of solvent and solid particles.

The (haloorganyl) alkoxysilane, additives and alcohol can be mixed with each other in any desired sequence or by any means at any target temperature and at any desired duration, and only then a sulfonating reagent is added.

(Haloorganyl) alkoxysilane, additives and a sulfonating reagent can be mixed with each other in any desired sequence or by any means at any target temperature and at any desired duration, and only then alcohol is added.

The sulfonating reagent, additives and alcohol can be mixed with each other in any desired sequence or by any means at any target temperature and at any desired duration, and only then (haloorganyl) alkoxysilane is added.

(Haloorganyl) alkoxysilane, alcohol and a sulfonating reagent can be mixed with each other in any desired sequence or by any means at any target temperature and at any desired duration, and only then additives are added.

Used aqueous sulfonating reagents can be introduced into the reaction in the form of solid particles or in solution.

Sulfurizing agents necessary for the reaction can be prepared before or during the reaction from sulfur-containing compounds.

Sulfurizing agents necessary for the reaction can be prepared before or during the reaction from metal hydroxides + sulfur, metal hydroxides + alkali metal hydrosulfides, metal hydroxides + sulfur + alkali metal hydrosulfides, metal hydroxides + H ₂ S + sulfur + alkali metal hydrosulfides or metal hydroxides + H ₂ S + sulfur + alkali metal sulfides.

Sulfurizing agents necessary for the reaction can be obtained before or during the reaction from alcoholates + sulfur, alcoholates + H ₂ S + sulfur or alcoholates + alkali metal hydrosulfides + sulfur.

Due to protonation under reaction conditions, sulfur-containing compounds can interact completely or not completely, reversibly or irreversibly with the formation of alkali metal hydrosulfides or H ₂ S.

Due to deprotonation under reaction conditions, sulfur-containing compounds can interact completely or not completely, reversibly or irreversibly with the formation of alkali metal sulfides or alkali metal hydrosulfides.

Protonation of sulfur compounds, from which alkali metal hydrosulfides are formed before or during the reaction, can occur due to H ₂ S and / or organic and / or inorganic acids.

The deprotonation of sulfur compounds, from which alkali metal sulfides are formed before or during the reaction, can occur due to organic and / or inorganic bases.

The deprotonation of H ₂ S, leading to the formation of alkali metal hydrosulfides before or during the reaction, can occur due to organic and / or inorganic bases.

Aqueous sulfonating reagents may include greater than 30, preferably greater than 40, particularly preferably greater than 50, even more preferably greater than 60 wt.% Sulfonating reagents.

In addition to water, aqueous sulfonating reagents may include additional secondary components in an amount of less than 50, preferably less than 30, particularly preferably less than 20, even more preferably less than 10 wt.%.

Additional secondary components of aqueous sulfonating reagents, in addition to water, may independently be alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, alkali metal sulfates, alkali metal bisulfates, alkali metal thiosulfates and / or alkali metal thiosulfates.

The molar amount of sulfonating reagents used may exceed the total molar amount of the (haloorganyl) alkoxysilane used by 1 to 50, preferably 5 to 30, particularly preferably 5 to 20, even more preferably 5 to 10 mol. %

Amounts of sulfonating reagents that are less than the stoichiometrically necessary amounts can lead to incomplete conversion. Therefore, either the product may be further contaminated with the starting material, or complex cleaning may be necessary in order to separate the starting materials and products from each other.

Primary, secondary or tertiary alcohols containing from 1 to 24, preferably from 1 to 6, particularly preferably from 1 to 4 carbon atoms, can be used as alcohol.

As the alcohol, aliphatic ethers of the formula HO- (CR ^IV ₂ ) -O-Alk or HO- (CR ^IV ₂ ) _y -O-Alk, or aliphatic polyethers of the formula HO- (CR ^IV ₂ O) _y -Alk can be used or HO- (CR ^IV ₂ —CR ^IV ₂ —Q) _y —Alk, where y is from 2 to 20, preferably from 2 to 10, particularly preferably from 3 to 6, R ^IV, independently of one another, is H or alkyl a group, preferably a CH ₃ group, a Alk is a branched or straight chain saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic monovalent C ₁ -C ₃₀ -, preferably particularly C ₂ -C ₂₀ -, particularly preferably C ₆ -C ₁₈ -, most preferably C ₁₀ -C ₁₈ -hydrocarbon group.

Primary, secondary or tertiary alcohols that can be used are methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, dodecanol, tetradecanol, hexadecanol and octadecanol. Aliphatic polyethers that can be used are HO- (CH ₂ —CH ₂ —O) _a —C _b H _{2b + 1} , where a is from 2 to 20, preferably from 2 to 10, particularly preferably from 2 to 8 , most preferably from 3 to 6, ab denotes from 1 to 30, preferably from 2 to 20, particularly preferably from 6 to 18, even more preferably from 10 to 18.

Primary alcohols may serve

HO- (CH ₂ —CH ₂ —O) ₂ —C ₆ H ₁₃ , HO- (CH ₂ —CH ₂ —O) ₃ —C ₆ H ₁₃ , HO- (CH ₂ —CH ₂ —O) ₄ —C ₆ H ₁₃ , HO- (CH ₂ —CH ₂ —O) ₅ —C ₆ H ₁₃ , HO- (CH ₂ —CH ₂ —O) ₆ —C ₆ H ₁₃ , HO- (CH ₂ —CH ₂ —O) ₇ —C ₆ H ₁₃ , HO- (CH ₂ —CH ₂ —O) ₈ —C ₆ H ₁₃ , HO- (CH ₂ —CH ₂ —O) ₉ —C ₆ H ₁₃ , HO- (CH ₂ —CH ₂ —O) ₂ —C ₁₀ H ₂₁ , HO- (CH ₂ —CH ₂ —O) ₃ —C ₁₀ H ₂₁ , HO- (CH ₂ —CH ₂ —O) ₄ —C ₁₀ H ₂₁ , HO- (CH ₂ —CH ₂ —O) ₅ —C ₁₀ H ₂₁ , HO- (CH ₂ —CH ₂ —O) ₆ —C ₁₀ H ₂₁ , HO- (CH ₂ —CH ₂ —O) ₇ —C ₁₀ H ₂₁ , HO- (CH ₂ —CH ₂ —O) ₈ —C ₁₀ H ₂₁ , HO- (CH ₂ —CH ₂ —O) ₉ —C ₁₀ H ₂₁ , HO- (CH ₂ —CH ₂ —O) ₂ —C ₁₃ H ₂₇ , HO- (CH ₂ —CH ₂ —O) ₃ —C ₁₃ H ₂₇ , HO- (CH ₂ —CH ₂ —O) ₄ —C ₁₃ H ₂₇ , HO- (CH ₂ —CH ₂ —O) ₅ —C ₁₃ H ₂₇ , HO- (CH ₂ —CH ₂ —O) ₆ —C ₁₃ H ₂₇ , HO- (CH ₂ —CH ₂ —O) ₇ —C ₁₃ H ₂₇ , HO- (CH ₂ —CH ₂ —O) ₈ —C ₁₃ H ₂₇ , HO- (CH ₂ —CH ₂ —O) ₉ —C ₁₃ H ₂₇ , HO- (CH ₂ —CH ₂ —O) ₂ —C ₁₅ H ₃₁ , HO- (CH ₂ —CH ₂ —O) ₃ —C ₁₅ H ₃₁ , HO- (CH ₂ -CH ₂ -O) ₄ -C ₁₅ H ₃₁ , HO- (CH ₂ —CH ₂ —O) ₅ —C ₁₅ H ₃₁ , HO- (CH ₂ —CH ₂ —O) ₆ —C ₁₅ H ₃₁ , HO- (CH ₂ —CH ₂ —O) ₇ —C ₁₅ H ₃₁ ,

HO- (CH ₂ -CH ₂ -O) ₈ -C ₁₅ H ₃₁ and HO- (CH ₂ -CH ₂ -O) ₉ -C ₁₅ H ₃₁

The amount of alcohol may be at least 0.1 vol.%, Preferably from 10 to 800, particularly preferably from 50 to 700, even more preferably from 100 to 500 vol.%, In terms of the silane components used.

Alcohol may include less than 20, preferably less than 10, particularly preferably less than 5, preferably preferably less than 1, even more preferably less than 0.1 wt.% Water.

As alcohol, you can use a mixture of alcohols.

The reaction can be carried out at temperatures ranging from 0 to 180, preferably in the range from 70 to 150, particularly preferably in the range from 70 to 125 ° C.

During the processing of raw products, alcoholic solvents can be removed under vacuum and at elevated temperatures. In order to isolate under vacuum at elevated temperature, not only a solvent, but also water, water-capturing substances (substances forming azeotropes) known to the person skilled in the art can be added and used. The water contained in the crude product can be removed from the crude product or the final product under vacuum at elevated temperature. To isolate the solvent, the azeotrope forming substance, and water, auxiliary substances and devices known to those skilled in the art can be used.

In a preferred embodiment, vertical tube evaporators, horizontal tube evaporators, inclined evaporators, falling film evaporators, plate-type evaporators, blown tube evaporators, rotary evaporators, centrifugal evaporators, screw evaporators, thin film evaporators and thin-section can be used.

The reaction can be carried out in reaction vessels or autoclaves that are corrosion resistant or insensitive to corrosion.

In a preferred embodiment, the reaction can be carried out in corrosion-resistant reaction vessels or autoclaves, for example, glass, Teflon, enamelled or clad steel, Hastelloy or tantalum.

A solvent / water mixture can be removed from the crude product suspension, preferably under reduced pressure, and the resulting suspension containing the obtained organosilane of general formula I can be separated from the solid material, preferably by centrifugation, decantation or filtration.

The solvent / water mixture can be removed under pressure from 800 to 10 mbar, preferably by distillation. The solvent / water mixture may contain ethanol.

The resulting suspension may include Me (Hal), for example NaCl, buffer salts and organosilanes of the general formula I.

The solvent can be removed from the crude product suspension, a mixture comprising organosilanes of the general formula (I) and solid Me (Na1) can be mixed with water containing at least one buffer, and the phases formed can be separated.

Processing the crude product suspension may include filtering and separating the solid components. Processing a suspension of the crude product may include distillation and separation of volatile components. Processing the suspension of the crude product may include first distillation and then filtration. Processing the suspension of the crude product may include first filtration and then distillation. Processing a suspension of a crude product may include first filtering, then distillation, and then further filtering.

The salt-containing suspension of the crude product contained after the reaction can be treated under atmospheric pressure or reduced pressure, preferably under reduced pressure in the range from 1 to 700, particularly preferably in the range from 5 to 500, even more preferably in the range from 10 to 250 mbar .

The salt-containing suspension of the product contained after the reaction can be treated at room temperature or elevated temperature, preferably in the range from 20 to 200, particularly preferably in the range from 40 to 150, even more preferably in the range from 50 to 100 ° C.

During processing, a mixture of product and solid material may form. During processing, a mixture of product and alcohol may form.

During processing, a mixture of product, alcohol and water may form. During processing, a mixture of product and water may form. During processing, a mixture of product, solid material and water may form. During processing, a mixture of the product, Me (Hal), for example sodium chloride, and water can form. During processing, a mixture of the product, Me (Hal), for example sodium chloride, alcohol and water, may form.

Water may be added to the mixture of the product and / or solid material and / or alcohol and / or water.

Water can be added in an amount of from 1 to 200, preferably from 1 to 100, particularly preferably from 5 to 75, even more preferably from 5 to 50 wt.% In terms of product.

Water can be demineralized water. Water may include a buffer, for example sodium bicarbonate or sodium carbonate. The buffer content in the water may be from 1 to 20, preferably from 2 to 5 wt.%.

The added water may have a pH in the range of 3 to 11, preferably in the range of 4 to 10, particularly preferably in the range of 5 to 9, even more preferably in the range of 7 and 9.

The pH of the added water can be adjusted with a buffer, for example NaHCO ₃ .

In a preferred embodiment, a solid material may be contained in the aqueous phase. In a preferred embodiment, the Me phase may contain a salt of Me (Hal), for example sodium chloride.

The product can be isolated from the phase-containing aqueous phase salt. After phase separation, the product can be isolated from the salt-containing aqueous phase. After the salt-containing phase is isolated, the product can be dried.

In a first preferred embodiment for the preparation of organosilanes of the general formula I, where X is SH, m is 1 and n is 1, alkali metal hydrosulfide can be used as the water-containing sulfonating reagent.

In this first embodiment, additives selected from the group consisting of H ₂ S, CO ₂ , (haloorgan) halosilane and a compound which is capable of reversibly or irreversibly releasing a proton to alkali metal alkoxides at pH in can be added to the reaction mixture before, during or after the reaction. ranges from 5 to 9.

In the preparation of organosilanes of the general formula I, wherein X is SH, before, during and / or upon completion of the reaction, additives can be added as additives which, in combination with alcohols, release organic or inorganic acids.

In the preparation of organosilanes of the general formula I, where X is SH, the amount of alcohol can be at least 10, preferably from 10 to 800, particularly preferably from 50 to 500, most preferably from 100 to 300 vol.%, Based on the silane components used.

Compounds that release inorganic acids in the presence of alcohols may be chlorosilanes. Chlorosilanes may include from 1 to 4 Si-Cl bonds per silicon atom. Chlorosilanes can be (CH ₃ ) SiCl ₃ , (CH ₃ ) ₂ SiCl ₂ , (CH ₃ ) ₃ SiCl, SiCl ₄ , HsiCl ₃ and H ₂ SiCl ₂ .

Compounds which are capable of reversibly or irreversibly releasing a proton to alkali metal alkoxides at a pH in the range of 5 to 9 can be, for example, organic or inorganic acids.

Organic acids can be compounds of the following starting configurations: alkyl-COOH, aryl-COOH, aralkyl-COOH, alkyl-S (O) ₂ OH, HOOC-alkylene-COOH, HOOC-aryl-COOH and HOOC-aralkyl-COOH.

Organic acids can be, for example, formic acid, acetic acid, propanoic acid, pivalic acid, isooctanoic acid, isononanoic acid, lauric acid (C12), myristic acid (C14), palmitic acid (C16), stearic acid (C18), oleic acid, linoleic acid, linolenic acid, benzoic acid, oxalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, 1,12-dodecanoic acid, aminoundecanoic acid, phthalic acid, terephthalic acid, maleic acid, fumar Wai acid, malonic acid, acrylic acid and methacrylic acid.

Inorganic acids can be, for example, compounds of the composition HCl, H ₂ SO ₄ , H ₃ PO ₄ , (alkali metal ion) H ₂ PO ₄ , (alkali metal ion) ₂ HPO ₄ , H ₂ CO ₃ , (alkali metal ion) HCO ₃ and (alkali metal ion) HSO ₄ . Preferred structural compounds (alkali metal ion) H ₂ PO ₄ can be KH ₂ PO ₄ and NaH ₂ PO ₄ . Preferred structural compounds (alkali metal ion) ₂ HPO ₄ can be K ₂ HPO ₄ and Na ₂ HPO ₄ . Preferred structural compounds (alkali metal ion) HCO ₃ can be KHCO ₃ and NaHCO ₃ . Preferred structural compounds (alkali metal ion) of HSO ₄ may be KHSO ₄ and NaHSO ₄ . The inorganic acid H ₂ CO ₃ can be obtained by passing CO ₂ through an aqueous reaction mixture.

Acidic or basic additives that are introduced into the reaction mixture before, during or at the end of the process may have the structure (alkali metal ion) H ₂ PO ₄ (alkali metal ion) (OH), (alkali metal ion) ₂ HPO ₄ (ion alkali metal) ₃ PO ₄ , (alkali metal ion) HCO ₃ , (alkali metal ion) ₂ CO ₃ , (alkali metal ion) ₂ SO ₄ and (alkali metal ion) HSO ₄ . Preferred structural compounds (alkali metal ion) H ₂ PO ₄ can be KH ₂ PO ₄ and NaH ₂ PO ₄ . Preferred structural compounds (alkali metal ion) ₂ HPO ₄ can be K ₂ HPO ₄ and Na ₂ HPO ₄ . Preferred structural compounds (alkali metal ion) HCO ₃ can be KHCO ₃ and NaHCO ₃ . Preferred structural compounds (alkali metal ion) of HSO ₄ may be KHSO ₄ and NaHSO ₄ .

The reaction for producing organosilanes of the general formula I, where X is SH, can preferably be carried out under increased pressure (> 0.5 bar, gauge pressure). The elevated pressure may range from 20 to 0.5, preferably from 15 to 0.5, particularly preferably from 10 to 0.5, even more preferably from 5 to 0.5 bar gauge pressure.

The reaction for the production of organosilanes of the general formula I, where X is SH, can preferably be carried out in a closed vessel and optionally in an inert gas.

The reaction for producing organosilanes of the general formula I, wherein X is SH, can preferably be carried out in the absence of air.

The reaction for the production of organosilanes of the general formula I, where X is SH, can preferably be carried out in such a way that the gas produced cannot escape from the reaction space.

Organosilanes of the general formula I may be:

3-mercaptopropyl (trimethoxysilane),

3-mercaptopropyl (dimethoxyhydroxysilane),

3-mercaptopropyl (triethoxysilane),

3-mercaptopropyl (diethoxyhydroxysilane),

3-mercaptopropyl (diethoxymethoxysilane),

3-mercaptopropyl (tripropoxysilane),

3-mercaptopropyl (dipropoxymethoxysilane),

3-mercaptopropyl (dipropoxyhydroxysilane),

3-mercaptopropyl (tridodecanoxysilane),

3-mercaptopropyl (didodecanoxyhydroxysilane),

3-mercaptopropyl (tritetradecanoxysilane),

3-mercaptopropyl (trihexadecanoxysilane),

3-mercaptopropyl (trioctadecanoxysilane),

3-mercaptopropyl (didodecanooxy) tetradecanoxysilane,

3-mercaptopropyl (dodecanoxy) tetradecanoxy (hexadecanoxy) silane,

3-mercaptopropyl (dimethoxymethylsilane),

3-mercaptopropyl (methoxymethylhydroxysilane),

3-mercaptopropyl (methoxydimethylsilane),

3-mercaptopropyl (hydroxydimethylsilane),

3-mercaptopropyl (diethoxymethylsilane),

3-mercaptopropyl (ethoxyhydroxymethylsilane),

3-mercaptopropyl (ethoxydimethylsilane),

3-mercaptopropyl (dipropoxymethylsilane),

3-mercaptopropyl (propoxymethylhydroxysilane),

3-mercaptopropyl (propoxymethylsilane),

3-mercaptopropyl (diisopropoxymethylsilane),

3-mercaptopropyl (isopropoxymethylsilane),

3-mercaptopropyl (dibutoxymethylsilane),

3-mercaptopropyl (butoxydimethylsilane),

3-mercaptopropyl (diisobutoxymethylsilane),

3-mercaptopropyl (isobutoxymethylhydroxysilane),

3-mercaptopropyl (isobutoxydimethylsilane),

3-mercaptopropyl (didodecanooxymethylsilane),

3-mercaptopropyl (dodecane oxydimethylsilane),

3-mercaptopropyl (ditetradecanoximethylsilane),

3-mercaptopropyl (tetradecanoximethylhydroxysilane),

3-mercaptopropyl (tetradecane oxydimethylsilane),

2-mercaptoethyl (trimethoxysilane),

2-mercaptoethyl (triethoxysilane),

2-mercaptoethyl (diethoxymethoxysilane),

2-mercaptoethyl (tripropoxysilane),

2-mercaptoethyl (dipropoxymethoxysilane,

2-mercaptoethyl (tridodecanoxysilane),

2-mercaptoethyl (tritetradecanoxysilane),

2-mercaptoethyl (trihexadecanoxysilane),

2-mercaptoethyl (trioctadecanoxysilane,

2-mercaptoethyl (didodecanoxy) tetradecanoxysilane,

2-mercaptoethyl (dodecanoxy) tetradecanoxy (hexadecanoxy) silane,

2-mercaptoethyl (dimethoxymethylsilane),

2-mercaptoethyl (methoxymethylhydroxysilane),

2-mercaptoethyl (methoxydimethylsilane),

2-mercaptoethyl (diethoxymethylsilane),

2-mercaptoethyl (ethoxydimethylsilane),

2-mercaptoethyl (hydroxydimethylsilane),

1-mercaptomethyl (trimethoxysilane),

1-mercaptomethyl (triethoxysilane),

1-mercaptomethyl (diethoxymethoxysilane),

1-mercaptomethyl (diethoxyhydroxysilane),

1-mercaptomethyl (dipropoxymethoxysilane),

1-mercaptomethyl (tripropoxysilane),

1-mercaptomethyl (trimethoxysilane),

1-mercaptomethyl (dimethoxymethylsilane),

1-mercaptomethyl (methoxydimethylsilane),

1-mercaptomethyl (diethoxymethylsilane),

1-mercaptomethyl (ethoxymethylhydroxysilane),

1-mercaptomethyl (ethoxydimethylsilane),

1,3-dimercaptopropyl (trimethoxysilane),

1,3-dimercaptopropyl (triethoxysilane),

1,3-dimercaptopropyl (tripropoxysilane),

1,3-dimercaptopropyl (tridodecanoxysilane),

1,3-dimercaptopropyl (tritetradecanoxysilane),

1,3-dimercaptopropyl (trihexadecanoxysilane),

2,3-dimercaptopropyl (trimethoxysilane),

2,3-dimercaptopropyl (triethoxysilane),

2,3-dimercaptopropyl (tripropoxysilane),

2,3-dimercaptopropyl (tridecaneoxysilane),

2,3-dimercaptopropyl (tritetradecanoxysilane),

2,3-dimercaptopropyl (trihexadecanoxysilane),

3-mercaptobutyl (trimethoxysilane),

3-mercaptobutyl (triethoxysilane),

3-mercaptobutyl (diethoxymethoxysilane),

3-mercaptobutyl (tripropoxysilane),

3-mercaptobutyl (dipropoxymethoxysilane),

3-mercaptobutyl (dimethoxymethylsilane),

3-mercaptobutyl (diethoxymethylsilane),

3-mercaptobutyl (dimethylmethoxysilane),

3-mercaptobutyl (dimethylethoxysilane),

3-mercaptobutyl (dimethylhydroxysilane),

3-mercaptobutyl (tridodecanoxysilane),

3-mercaptobutyl (tritetradecanoxysilane),

3-mercaptobutyl (trihexadecanoxysilane),

3-mercaptobutyl (didodecanooxy) tetradecanoxysilane,

3-mercaptobutyl (dodecanoxy) tetradecanoxy (hexadecanoxy) silane,

3-mercapto-2-methylpropyl (trimethoxysilane),

3-mercapto-2-methylpropyl (triethoxysilane),

3-mercapto-2-methylpropyl (diethoxymethoxysilane),

3-mercapto-2-methylpropyl (tripropoxysilane),

3-mercapto-2-methylpropyl (dipropoxymethoxysilane),

3-mercapto-2-methylpropyl (tridodecanoxysilane),

3-mercapto-2-methylpropyl (tritetradecanoxysilane),

3-mercapto-2-methylpropyl (trihexadecanoxysilane),

3-mercapto-2-methylpropyl (trioctadecanoxysilane),

3-mercapto-2-methylpropyl (didodecanooxy) tetradecanoxysilane,

3-mercapto-2-

methylpropyl (dodecanoxy) tetradecanoxy (hexadecanoxy) silane,

3-mercapto-2-methylpropyl (dimethoxymethylsilane),

3-mercapto-2-methylpropyl (methoxymethylsilane),

3-mercapto-2-methylpropyl (diethoxymethylsilane),

3-mercapto-2-methylpropyl (ethoxymethylsilane),

3-mercapto-2-methylpropyl (hydroxydimethylsilane),

3-mercapto-2-methylpropyl (dipropoxymethylsilane),

3-mercapto-2-methylpropyl (propoxymethylsilane),

3-mercapto-2-methylpropyl (diisopropoxymethylsilane),

3-mercapto-2-methylpropyl (isopropoxymethylsilane),

3-mercapto-2-methylpropyl (dibutoxymethylsilane),

3-mercapto-2-methylpropyl (butoxymethylsilane),

3-mercapto-2-methylpropyl (diisobutoxymethylsilane),

3-mercapto-2-methylpropyl (isobutoxydimethylsilane),

3-mercapto-2-methylpropyl (didodecanooxymethylsilane),

3-mercapto-2-methylpropyl (dodecanooxydimethylsilane),

3-mercapto-2-methylpropyl (ditetradecanooxymethylsilane),

3-mercapto-2-methylpropyl (tetradecane oxydimethylsilane),

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₆ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C _1H H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] (MeO) ₂ Si (CH ₂ ) ₃ 3H,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] (MeO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (MeO) Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(H ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₆ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] (EtO) ₂ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (EtO) Ei (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] ₂ (EtO) Ei (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] ₂ (EtO) Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] ₂ (EtO) Ei (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₂ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₃ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₄ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₅ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₉ H ₁₉ O- (CH ₂ -CH ₂ O) ₆ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₂ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₃ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₄ ] ₃ Si (CH ₂ H ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₅ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₂ H ₂₅ O- (CH ₂ -CH ₂ O) ₆ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₂ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₃ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₄ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₅ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₃ H ₂₇ O- (CH ₂ -CH ₂ O) ₆ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₂ ] ₃ SiHCH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₃ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₄ ] ₃ SiHCH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₅ ] ₃ Si (CH ₂ ) ₃ SH,

[(C ₁₄ H ₂₉ O- (CH ₂ -CH ₂ O) ₆ ] ₃ SiHCH ₂ ) ₃ SH.

Compounds of the general formula III may be used as (haloorganyl) halosilanes for the preparation of organosilanes of the general formula I, where X is SH

,

,

in which Hal, R and R ″ have the above meanings, and R ″ ″ are independently R or Hal.

In a preferred embodiment, (chloroorganyl) chlorosilanes may be used as (haloorganyl) halosilanes.

So, for example, as (haloorganyl) halosilanes can be used

3-chlorobutyl (trichlorosilane),

3-chloropropyl (trichlorosilane),

2-chloroethyl (trichlorosilane),

1-chloromethyl (trichlorosilane),

3-chlorobutyl (dichloromethoxysilane),

3-chloropropyl (dichloromethoxysilane),

2-chloroethyl (dichloromethoxysilane),

1-chloromethyl (dichloromethoxysilane),

3-chlorobutyl (dichloroethoxysilane),

3-chloropropyl (dichloroethoxysilane),

2-chloroethyl (dichloroethoxysilane),

1-chloromethyl (dichloroethoxysilane),

3-chlorobutyl (chlorodiethoxysilane),

3-chloropropyl (chlorodiethoxysilane),

2-chloroethyl (chlorodiethoxysilane),

1-chloromethyl (chlorodiethoxysilane),

3-chlorobutyl (chlorodimethoxysilane),

3-chloropropyl (chlorodimethoxysilane),

2-chloroethyl (chlorodimethoxysilane),

1-chloromethyl (chlorodimethoxysilane),

3-chlorobutyl (dichloromethylsilane),

3-chloropropyl (dichloromethylsilane),

2-chloroethyl (dichloromethylsilane),

1-chloromethyl (dichloromethylsilane),

3-chlorobutyl ((chloro -) (methyl-) methoxysilane),

3-chloropropyl ((chloro -) (methyl-) methoxysilane),

2-chloroethyl ((chloro -) (methyl-) methoxysilane),

1-chloromethyl ((chloro -) (methyl-) methoxysilane),

3-chlorobutyl ((chloro -) (methyl-) ethoxysilane),

3-chloropropyl ((chloro -) (methyl-) ethoxysilane),

2-chloroethyl ((chloro -) (methyl-) ethoxysilane),

1-chloromethyl ((chloro -) (methyl-) ethoxysilane),

3-chlorobutyl (chlorodimethylsilane),

3-chloropropyl (chlorodimethylsilane),

2-chloroethyl (chlorodimethylsilane) and

1-chloromethyl (chlorodimethylsilane).

The (haloorgan) halosilane may be a (haloorgan) halosilane of the general formula III or a mixture of (haloorganyl) chlorosilanes of the general formula III.

(Haloorganyl) alkoxysilane and (haloorganyl) chlorosilane can be used in a molar ratio of from 1: 0.00001 to 1: 0.8, preferably from 1: 0.00001 to 1: 0.5, particularly preferably from 1: 0.00001 to 1: 0.15, even more preferably from 1: 0.00001 to 1: 0.09.

Depending on the device used and the desired effects, for example, reaction selectivity, reaction time, reactor productivity, the reaction of (haloorgan) alkoxy silane and (haloorgan) chlorosilane together, the reactor material and the process sequence, a mixture of (haloorgan) alkoxysilane and (haloorgan) chlorosilane in the preferred variant can be obtained before adding alkali metal hydrosulfide.

The quality and type of composition of the mixture of (haloorgan) alkoxysilane and (haloorgan) chlorosilane can be estimated on the basis of the amount and type of Si-halide bonds capable of hydrolyzing in the mixture.

The amount of hydrolyzable Si halide in the aforementioned mixtures of (haloorganyl) alkyloxysilane and (haloorganyl) chlorosilane mixtures, which can be determined by the above analysis method, can range from 2 to 800,000, preferably from 10 to 80,000, particularly preferably from 10 to 40,000 mg / kg.

The amount of hydrolyzable Si halide in the above mixtures of (haloorganyl) alkoxysilane and (haloorganyl) chlorosilane, which can be determined by the above analysis method, can be in the range from 2 to 800000, preferably in the range from 500 to 800000, particularly preferably in the range from 5000 up to 800,000, even more preferably in the range of 50,000 to 800,000 mg / kg.

The amount of hydrolyzable halide is determined according to the following method: in a 150 ml beaker, 80 ml of ethanol and 10 ml of acetic acid are added to not more than 20 g of the sample. The halide content is determined by potentiographic titration with a solution of silver nitrate (at a concentration of (AgNO ₃ ) of 0.01 mol / l).

Preferred molar ratios of mixtures of (haloorgan) alkoxysilanes and (haloorgan) halosilanes may depend, inter alia, on the number of Si-halide functional groups of the selected (haloorganyl) halosilanes.

For example, in the reaction of 3-chloropropyl (trimethoxysilane) or 3-chloropropyl (triethoxysilane) and 3-chloropropyl (trichlorosilane), a molar ratio of from 1: 0.00001 to 1: 0.03 can be used in a preferred embodiment.

Thus, for example, in the reaction of 3-chloropropyl (methyldimethoxysilane) or 3-chloropropyl (methyldiethoxysilane) and 3-chloropropyl (methyldichlorosilane), a molar ratio of from 1: 0.00001 to 1: 0.045 can be preferably used.

For example, in the reaction of 3-chloropropyl (dimethylmethoxysilane) or 3-chloropropyl (dimethylethoxysilane) and 3-chloropropyl (dimethylchlorosilane), a molar ratio of from 1: 0.00001 to 1: 0.09 can be used in a preferred embodiment.

(Haloorganyl) alkoxysilane and (haloorganyl) halosilane can be mixed with each other in any desired sequence or by any means at any target temperature and any required duration, and only then alcohol and alkali metal hydrosulfide are added simultaneously or sequentially.

(Haloorganyl) halosilanes, alkali metal hydrosulfide and alcohol can be mixed with each other in any desired sequence or by any means at any target temperature and for any desired duration, and only then (haloorganyl) alkoxysilane is added.

(Haloorganyl) alkoxysilane, alkali metal hydrosulfide and alcohol can be mixed with each other in any desired sequence or by any means at any target temperature and any desired duration, and only then (haloorganyl) halosilane is added.

(Haloorganyl) alkoxysilane, alcohol and additives can be mixed with each other in any desired sequence or by any means at any target temperature and any desired duration, and only then alkali metal hydrosulfide is added.

Additives, alkali metal hydrosulfide and alcohol can be mixed with each other in any desired sequence or by any means at any target temperature and any required duration, and only then (haloorganyl) alkoxysilane is added.

(Haloorganyl) alkoxysilane, alkali metal hydrosulfide and alcohol can be mixed with each other in any desired sequence or by any means at any target temperature and any required duration, and only then additives are added.

(Haloorganyl) alkoxysilane, alkali metal hydrosulfide and additives can be mixed with each other in any necessary sequence or by any means at any target temperature and any necessary duration, and only then alcohol is added.

Compounds of general formula I, wherein X is SH,

in a preferred embodiment, can be obtained by reaction of an aqueous alkali metal hydrosulfide with (haloorgan) alkoxysilanes of the general formula II

in alcohol in a closed vessel in the absence of air and under increased pressure in the presence of additives.

This reaction can preferably be carried out in the presence of H ₂ S.

The amount of added and / or released H ₂ S in the preparation of compounds of general formula I, where X is SH, may be less than 500, preferably less than 100, particularly preferably less than 50, even more preferably less than 15 mol%, based on the amount of haloorganyl used ( alkoxysilane).

In the preparation of compounds of general formula I, where X is SH, the crude product yield of the method according to the invention can be greater than 80, preferably greater than 85, particularly preferably greater than 90, even more preferably greater than 95%, based on the theoretical yield, taking into account the totality ( haloorgan) alkoxysilane and (halo organic) halosilanes.

The yield of crude product can be determined gravimetrically as the sum of all liquid compounds isolated after removal of solvent and solid particles.

In the preparation of compounds of general formula I, where X is SH, the amount of R ₂ (R'O) Si- (R ″) -S- (R ″) -Si (OR ′) R ₂ formed as a by-product may be less than 15, preferably less than 10, particularly preferably less than 8, even more preferably less than 5 wt.% based on the amount of crude product.

In the preparation of compounds of general formula I, where X is SH, lithium hydrosulfide (LiSH), sodium hydrosulfide (NaSH), potassium hydrosulfide (KSH) and cesium hydrosulfide (CsSH) can be used independently as water-containing sulfonating reagents.

The aqueous alkali metal hydrosulfides used in the preparation of the compounds of general formula I, where X is SH, can be introduced into the reaction in the form of solid particles or in solution.

The alkali metal hydrosulphides required for the reaction in the preparation of compounds of the general formula I, wherein X is SH, can be prepared before or during the reaction from sulfur-containing compounds as described above.

Sulfur-containing compounds from which the alkali metal hydrosulfides are prepared before or during the reaction can be H ₂ S, Me ₂ S alkali metal sulfides or Me ₂ S _g alkali metal polysulfides, preferably Li ₂ S, Na ₂ S, K ₂ S, Na ₂ S ₂ , Na ₂ S ₃ , Na ₂ S ₄ , K ₂ S ₂ , K ₂ S ₃ or K ₂ S ₄ .

In the preparation of compounds of general formula I, where X is SH, sulfur-containing compounds from which alkali metal hydrosulfides are prepared before or during the reaction can react fully or not fully, reversibly or irreversibly due to protonation to form alkali metal hydrosulfides.

In the preparation of compounds of general formula I, where X is SH, the protonation of sulfur compounds from which alkali metal hydrosulfides are formed before or during the reaction can occur with H ₂ S and / or organic and / or inorganic acids.

In the preparation of compounds of general formula I, where X is SH, aqueous alkali metal hydrosulfides may include more than 3, preferably more than 5, particularly preferably more than 10, even more preferably more than 12, most preferably more than 15 wt.% Water.

In the preparation of compounds of general formula I, where X is SH, aqueous alkali metal hydrosulfides may include more than 50, preferably more than 60, particularly preferably more than 65, even more preferably more than 70 wt.% Alkali metal hydrosulfide.

In the preparation of compounds of general formula I, where X is SH, aqueous alkali metal hydrosulfides may include, in addition to water, other secondary components in an amount of less than 50, preferably less than 30, particularly preferably less than 20, most preferably less than 10 wt.%.

In addition to water, other secondary components of aqueous alkali metal hydrosulfides can be alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, alkali metal sulfides, alkali metal sulfates, alkali metal bisulfates, alkali metal thiosulfates and / or acid thiosulfates alkali metals.

These additional secondary components of aqueous alkali metal hydrosulfides may be inert or reactive with respect to the starting materials and / or products used in the preparation of compounds of general formula I, where X is SH.

In the preparation of compounds of the general formula I, where X is SH, the molar amount of the alkali metal hydrosulfide used can exceed the total molar amounts of the (haloorgan) alkoxysilane and the (haloorgan) halosilane used by 1 to 50, preferably 5 to 30, especially preferably between 5 and 20%.

In the preparation of compounds of general formula I, where X is SH, amounts of alkali metal hydrosulfide that are less than the stoichiometrically necessary amounts can lead to an incomplete reaction. Therefore, either the product may be further contaminated with the starting material, or complex separation will be required to separate the starting materials and products.

In the preparation of compounds of general formula I, where X is SH, the reaction temperature, which in each case is optimal, taking into account the yield of the target product and the use of the reaction volume, can be varied as a function of the structure of the (haloorgan) alkoxysilane used and the alcohol used as solvent .

So, for example, in the preparation of compounds of general formula I, where X is SH, it may be preferable, taking into account the duration of the reaction, the amount of by-product and the pressure created in the reactions in methanol, the reaction temperature in the range from 40 to 95, more preferably in the range from 60 to 95 ° C.

So, for example, in the preparation of compounds of general formula I, where X is SH, it may be preferable, taking into account the duration of the reaction, the amount of by-product and the pressure created in the reactions in ethanol, the reaction temperature in the range from 50 to 130, more preferably in the range from 75 to 130 ° C.

In the preparation of compounds of general formula I, where X is SH, a closed container may preferably be a reaction vessel, which is known in the industry and which makes it possible to carry out the process under pressures up to 20 bar and at temperatures up to 200 ° C. Such a closed container may have circulation means for heating / cooling.

In the preparation of compounds of general formula I, where X is SH, due to the choice of reaction conditions, the amount of by-product can be less than 20, preferably less than 15, particularly preferably less than 10 mol%.

In addition to mercaptoorganylsilane compounds, the target according to condition X is SH, corresponding monosulfanes or disulfanes and, depending on the structure of the monomeric mercaptoorganylsilane compounds, various combinations of dimeric or oligomeric siloxanes can be formed as by-products from end products or from products with starting materials.

In a second preferred embodiment, for the preparation of organosilanes of the general formula I, where X is S, am is 3.5 to 4.5, Me ₂ S and sulfur can be used as the water-containing sulfonating reagent.

The reaction can be carried out in the presence of a solvent or a mixture of solvents and additives.

The aqueous sulfonating reagents that can be used are sulfides of ammonium, alkali metals and alkaline earth metals and their polysulfides or mixtures thereof. In a preferred embodiment, ammonium, lithium, sodium, potassium and cesium sulfonating reagents may be used as aqueous sulfonating reagents. In a particularly preferred embodiment, Na ₂ S hydrate or K ₂ S hydrate can be used as aqueous sulfonating reagents.

In this second embodiment, Me ₂ S may include more than 10, preferably more than 15, particularly preferably more than 20, even more preferably more than 30 wt.% Water.

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, water-containing sulfonating agents may include, in addition to water, other secondary components in an amount of less than 50, preferably less than 30, particularly preferably less than 20 , even more preferably less than 10 wt.%.

In the preparation of organosilanes of the general formula I, where X is S and m is from 3.5 to 4.5, in addition to water, alkali metal carbonates, alkali metal bicarbonates, hydroxides can independently serve as other secondary components of aqueous sulfonating reagents. alkali metals, alkali metal sulfates, alkali metal bisulfates, alkali metal phosphates, alkali metal acid phosphates, alkali metal primary phosphates, alkali metal thiosulfates and / or alkaline acid thiosulfates Ferrous materials.

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, the molar amount of the sulfonating reagent used may exceed the molar amount of the (haloorgan) alkoxysilane used by 0.1 to 50, preferably by 0.1 to 30, particularly preferably 0.1 to 5 mol%.

In the preparation of organosilanes of the general formula I, where X is S, and m is from 3.5 to 4.5, amounts of a sulfonating reagent, which are less than the stoichiometrically necessary amounts, can lead to incomplete conversion. Therefore, either the product is further contaminated with the starting material, or complex processing will be necessary in order to separate the starting materials and products from each other.

Sulfur may be added in the form of powdered sulfur or sulfur granules, or in liquid form.

In this second embodiment, the solvent or mixture of solvents in the preferred embodiment, can be an organic solvent or mixture of solvents, including organic solvents. Solvents or solvent mixtures may be, for example, alcohols or water-containing alcohols. The water content in the solvent or mixture of solvents may be from 0.1 to 50, preferably from 0.1 to 25, particularly preferably from 0.1 to 10, even more preferably from 0.1 to 5 wt.%.

In the preparation of organosilanes of the general formula I, where X is S and m is from 3.5 to 4.5, the amount of alcohol can be at least 5, preferably from 10 to 300, particularly preferably from 10 to 100, even more preferably from 10 to 25 vol.% In terms of the used silane component or silane components.

In the preparation of organosilanes of the general formula I, where X is S, and m is from 3.5 to 4.5, additives can be introduced independently into the reaction mixture before, during and upon completion of the reaction. In a preferred embodiment, the additives are administered before the reaction.

Additives can be (alkali metal ion) H ₂ PO ₄ , (alkali metal ion) ₂ HPO ₄ , (alkali metal ion) ₃ PO ₄ , (alkali metal ion) HCO ₃ , (alkali metal ion) ₂ CO ₃ , (ion alkali metal) ₂ SO ₄ and (alkali metal ion) HSO ₄ . Suitable additives may also be the corresponding alkaline earth metal salts.

The reaction for the preparation of organosilanes of the general formula I, wherein X is S and a m is from 3.5 to 4.5, can preferably be carried out in the absence of air.

In this second embodiment, the organosilanes of general formula I can be mixtures of organosilanes of general formula I having an average sulfur chain length, i.e. m, component from 3.5 to 4.5, and these organosilanes may have sulfur chains from S1 to S12, for example

in the case of [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S _m :

[(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S, [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₂ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₃ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₄ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₅ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₆ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₇ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₈ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₉ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ Si ₁₀ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₁ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₂ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S,

in the case of [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S _m :

[(EtO) ₃ Si (CH _{2) 3] 2} S _2, [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₃ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₄ , [(EtO) ₃ Si (CH _{2) 3] 2} S _5, [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₆ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₇ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₈ , [(EtO) ₃ Si (CH _{2) 3] 2} S _9, [(EtO) ₃ Si (CH _{2) 3] 2} Si _10, [(EtO) ₃ Si (CH _{2) 3] 2} S _11, [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₂ ,

in the case of [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S _m :

[(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S, [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₂ , [(C ₃ H ₇ O) ₃ Si (CH _{2) 3] 2} S _3, [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₄ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₅ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₆ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₇ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₈ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₉ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₀ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₁ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₂

Organosilanes of the general formula I may be:

[(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S _m , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S _m , [(C ₃ H ₇ O) ₃ Si (CH _{2) 3] 2} S _m,

[(C ₁₂ H ₂₅ O) ₃ Si (CH ₂ ) S _m (CH ₂ ) ₃ Si (C ₁₂ H ₂₅ O) ₃ ],

[(C ₁₄ H ₂₉ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₄ H ₂₉ O) ₃ ],

[(C ₁₆ H ₃₃ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₆ H ₃₃ O) ₃ ],

[(C ₁₈ H ₃₇ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₈ H ₃₇ O) ₃ ],

[(C ₁₂ H ₂₅ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₂ H ₂₅ O) ₃ ],

[(C ₁₄ H ₂₉ O) ₃ Si (CH ₂ ) ₃ ] S _m (CH ₂ ) ₃ Si (C ₁₄ H ₂₉ O) ₃ ],

[(C ₁₆ H ₃₃ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₆ H ₃₃ O) ₃ ],

[(C ₁₈ H ₃₇ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₈ H ₃₇ O) ₃ ],

[(C ₁₂ H ₂₅ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) ₂ ],

[(C ₁₂ H ₂₅ O) (C ₁₄ H ₂₉ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) (C ₁₄ H ₂₉ O)],

[(C ₁₂ H ₂₅ O) (C ₁₄ H ₂₁ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) (C ₁₂ H ₂₅ O)],

[(C ₁₂ H ₂₅ O) (C ₁₆ H ₃₃ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) (C ₁₆ H ₃₃ O)],

[(C ₁₂ H ₂₅ O) (C ₁₈ H ₃₇ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) - (C ₁₂ -H ₂₅ O) (C ₁₈ H ₃₇ O)],

[(C ₁₂ H ₂₅ O) (C ₁₈ H ₃₇ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) - (C ₁₈ H ₃₇ O)],

[(C ₁₄ H ₂₉ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₄ H ₂₉ O) ₂ ],

[(C ₁₄ H ₂₉ O) (C ₁₆ H ₃₃ O) (CH ₃₎ Si (CH _{2) 3]} S _m [(CH _{2) 3} Si (CH ₃₎ (C ₁₄ H ₂₉ O) - (C ₁₆ H ₃₃ O)],

[(C ₁₄ H ₂₉ O) (C ₁₈ H ₃₇ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₄ H ₂₉ O) - (C ₁₈ H ₃₇ O)],

[(C ₁₆ H ₃₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₆ H ₃₃ O) ₂ ],

[(C ₁₆ H ₃₃ O) (C ₁₈ H ₃₇ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₆ H ₃₃ O) - (C ₁₈ H ₃₇ O)],

[(C ₁₈ H ₃₇ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₈ H ₃₇ O) ₂ ],

[(C ₁₂ H ₂₅ O) (CH _{3) 2} Si (CH _{2) 3]} S _m [(CH _{2) 3} Si (CH _{3) 2} (C ₁₂ H ₂₅ O)],

[(C ₁₂ H ₂₅ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₄ H ₂₉ O)],

[(C ₁₂ H ₂₅ O) (CH _{3) 2} Si (CH _{2) 3]} S _m [(CH _{2) 3} Si (CH _{3) 2} (C ₁₆ H ₃₃ O)]

[(C ₁₂ H ₂₅ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₈ H ₃₇ O)],

[(C ₁₄ H ₂₉ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₄ H ₂₉ O)],

[(C ₁₄ H ₂₉ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₆ H ₃₃ O)],

[(C ₁₄ H ₂₉ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₈ H ₃₇ O)],

[(C ₁₆ H ₃₃ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₆ H ₃₃ O)],

[(C ₁₆ H ₃₃ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₈ H ₃₇ O)]

and

[(C ₁₈ H ₃₇ O) (CH _{3) 2} Si (CH _{2) 3]} S _m [(CH _{2) 3} Si (CH _{3) 2} (C ₁₈ H ₃₇ O)],

where m is from 3.5 to 4.5.

Compounds of general formula I, wherein X is S and m is 3.5 to 4.5

in a preferred embodiment, can be obtained by the reaction of aqueous sulfonating reagents with (haloorgan) alkoxysilanes of General formula II

in an organic solvent or mixture of solvents, which may include water, for example alcohol, in an open or closed vessel, optionally under pressure and in the absence of air. In a particularly preferred embodiment, the reaction of aqueous sulfonating reagents with (haloorgan) alkoxysilanes of the general formula II

can be carried out in an open vessel in the absence of air under the pressure created under these conditions.

The reaction temperature, which in each case is optimal, taking into account the yield of the target product, can be varied depending on the structure of the used (haloorgan) alkoxysilane and alcohol used as a solvent, taking into account the type and quantity.

The reaction temperature may range from room temperature to the boiling point of the solvent used or the mixture of solvents. The reaction temperature is preferably in the range of 20 ° C. to the boiling point of the solvent used or the mixture of solvents; a particularly preferred reaction temperature is in the range of 40 to 80, even more preferably in the range of 60 to 70 ° C.

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, the product yield of the process according to the invention can be greater than 80, preferably greater than 85, particularly preferably greater than 90, even more preferably greater than 98 % in terms of theoretical yield, taking into account (haloorgan) alkoxysilane.

In the preparation of organosilanes of the general formula I, where X is S and m is from 3.5 to 4.5, the yield of the crude product can be determined gravimetrically as the sum of all isolated liquid compounds after solvents or solvent mixtures and solid particles are removed .

In the preparation of organosilanes of general formula I, where X is S, am is from 3.5 to 4.5, the composition of compounds or mixtures of compounds of general formula I, where X is S, am is from 3.5 to 4.5, can affect the active and targeted way by choosing the composition of the mixtures (haloorgan) alkoxysilanes used, sulfonating agents and alcohol, the amount of alcohol and additives.

A mixture of the corresponding (haloorgan) alkoxysilane and additives used in the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, can be obtained before adding sulfonating reagents, depending on the device used and the target effects, which in some cases can be influenced independently of each other, for example, the selectivity of the reaction, the duration of the reaction, the performance of the reactor, the reaction of (haloorgan) alkoxysilane and a sulfonating reagent with each other, the value of m Ovium X is S _m , a reaction of an alkali metal sulfide and sulfur, a reaction material or a process sequence.

A mixture of the corresponding sulfonating reagents, sulfur and additives used in the preparation of organosilanes of the general formula I, where X is S and m is from 3.5 to 4.5, can be obtained before adding (haloorgan) alkoxysilane depending on the device used and the target effects that in some cases can be influenced independently of each other, the material of the reactor or the process sequence.

The quality of the (haloorganyl) alkoxysilanes used in the preparation of organosilanes of the general formula I, where X is S and a m is from 3.5 to 4.5, can be estimated based on the number of Si-halide bonds capable of hydrolysis.

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, the amount of Si-halide capable of hydrolyzing in (haloorganyl) alkoxysilane of formula II, which can be determined by the above analysis method, can be in the range 2 to 10,000, preferably in the range of 10 to 1000, particularly preferably in the range of 10 to 100, even more preferably in the range of 10 to 50 mg / kg.

The amount of hydrolyzable halide in mixtures comprising haloorgan (alkoxysilane) and additives used in the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, is determined according to the following method: in a 150-milliliter beaker 80 ml of ethanol and 10 ml of acetic acid are added to no more than 20 g of the sample. The halide content is determined by potentiographic titration with a solution of silver nitrate (at a concentration of (AgNO ₃ ) of 0.01 mol / l).

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, (haloorgan) alkoxysilane and the additives can be mixed together in any desired sequence or by any means at any target temperature and any desired duration, and only then alcohol and sulfonating agents are added simultaneously or sequentially.

In the preparation of organosilanes of the general formula I, where X is S and m is from 3.5 to 4.5, additives, sulfonating reagents and alcohol can be mixed together in any desired sequence or by any means at any target temperature and any required duration and only then (haloorganyl) alkoxysilane is added.

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, (haloorgan) alkoxysilane, sulfonating reagents and alcohol can be mixed together in any desired sequence or by any means at any target temperature and at any necessary duration, and only after that add additives.

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, (haloorgan) alkoxysilane, sulfonating reagents and additives can be mixed together in any desired sequence or by any means at any target temperature and at any necessary duration, and only after that add alcohol.

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, sulfonating reagents and additives can be mixed together in any desired sequence or by any means at any target temperature and at any desired duration, and only then alcohol and (haloorganyl) alkoxysilane are added simultaneously or sequentially.

Water-containing sulfonating reagents, of which Na ₂ S hydrate and K ₂ S hydrate are used in a particularly preferred embodiment, can be metered into the reaction mixture before and / or during the reaction.

Water-containing sulfonating reagents used in the preparation of organosilanes of the general formula I, where X is S, a m is from 3.5 to 4.5, can be introduced into the reaction in the form of solid particles or in solution;

The aqueous sulfonating reagents required for the reaction in the preparation of organosilanes of the general formula I, where X is S and m is from 3.5 to 4.5, can be prepared before or during the reaction from sulfur-containing compounds.

Sulfur-containing compounds from which sulfonating reagents are prepared prior to or during the reaction in the preparation of organosilanes of the general formula I, where X is S, am is 3.5 to 4.5, may be sulfur, alkali metal sulfides Me ₂ S or alkaline polysulfides metals Me ₂ S _g , preferably Na ₂ S, K ₂ S, Na ₂ S ₂ , Na ₂ S ₃ , Na ₂ S ₄ , K ₂ S ₂ , K ₂ S ₃ or K ₂ S ₄ .

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, to obtain the products of the interaction of Me ₂ S or Me ₂ S _g and sulfur, raw materials that contain more than 30 can be used independently preferably more than 40, particularly preferably more than 50, most preferably more than 59 wt.% Me ₂ S or which contain more than 20, preferably more than 30, particularly preferably more than 40, even more preferably more than 50 wt.% Me ₂ S _g .

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, the reaction vessel may preferably be a reaction vessel, which is known in the industry and makes it possible to carry out the process under pressures from 0 to 10 bar and at temperatures up to 200 ° C. This reaction container may have circulation means for heating / cooling.

In the preparation of organosilanes of the general formula I, where X is S, and m is from 3.5 to 4.5, the number of by-products due to the choice of reaction conditions can be less than 10, preferably less than 5, particularly preferably less than 2 mol%.

In the preparation of organosilanes of the general formula I, where X is S, am is from 3.5 to 4.5, the amount of residual haloorgan (alkoxysilane) starting material, due to the choice of reaction conditions, can be less than 10, preferably less than 5, especially preferably less than 2, more preferably less than 1.5 wt.%.

In this second embodiment, the solvent / water mixture can be removed from the crude product suspension, preferably under reduced pressure, and the resulting suspension containing the organosilane of general formula I that is formed can be separated from the solid material, preferably by centrifugation, decantation or filtration.

The solvent / water mixture can be removed under pressure from 800 to 10 mbar, preferably by distillation. The solvent / water mixture may contain ethanol.

The resulting suspension may include Me (Hal), for example NaCl, buffer salts and organosilanes of the general formula I.

The solvent may be removed from the crude product suspension, the mixture comprising organosilanes of the general formula (I) and solid Me (Hal) may be mixed with water containing at least one buffer, and the phases formed may be separated.

Processing a slurry of a crude product may include filtering and removing solid components. Processing a suspension of the crude product may include distillation and removal of volatile components. Such processing of a slurry of a crude product may include first distillation and then filtration. Processing the suspension of the crude product may include first filtration and then distillation. Processing the suspension of the crude product may include first filtering, then distillation, and then further filtering.

The salt-containing suspension of the crude product present after the reaction can be treated under atmospheric pressure or reduced pressure, preferably under reduced pressure in the range from 1 to 700, particularly preferably in the range from 5 to 500, even more preferably in the range from 10 to 250 mbar .

The salt-containing suspension of the product contained after the reaction can be treated at room temperature or elevated temperature, preferably in the range from 20 to 200, particularly preferably in the range from 40 to 150, even more preferably in the range from 50 to 100 ° C.

During processing, a mixture of product and solid material may form. During processing, a mixture of product and alcohol may form. During processing, a mixture of product, alcohol and water may form. During processing, a mixture of product and water may form. During processing, a mixture of product, solid material and water may form. During processing, a mixture of the product, Me (Hal), for example sodium chloride, and water can form. During processing, a mixture of the product, Me (Hal), for example sodium chloride, alcohol and water, may form.

Water may be added to the mixture of the product and / or solid material and / or alcohol and / or water.

Water can be added in an amount of from 1 to 200, preferably from 1 to 100, particularly preferably from 5 to 75% by weight, even more preferably from 5 to 50% by weight, based on the product.

Water may be demineralized water. Water may include a buffer, for example sodium bicarbonate or sodium carbonate. The buffer content in the water may be from 1 to 20, preferably from 2 to 5 wt.%.

The added water may have a pH in the range of 3 to 11, preferably in the range of 4 to 10, particularly preferably in the range of 5 to 9, even more preferably in the range of 7 to 9.

The pH of the added water can be adjusted with a buffer, for example NaHCO ₃ .

In a preferred embodiment, a solid material may be contained in the aqueous phase. In a preferred embodiment, the Me phase may contain a salt of Me (Hal), for example sodium chloride.

The product can be isolated from the phase-containing aqueous phase salt. After phase separation, the product can be isolated from the salt-containing aqueous phase. After isolation from the salt phase, the product can be dried.

In a third preferred embodiment, for the preparation of organosilanes of general formula I, where X is S, am is from 1.5 to 4.5, preferably m is from 1.8 to 2.5, or m is from 3.4 to 4.0, particularly preferably m is from 2.0 to 2.3 or m is from 3.6 to 3.85, even more preferably m is from 2.05 to 2.2 or m is from 3.65 to 3.8, water-containing sulphurization reagents as may be used hydrosulfides of alkali metal Me ₂ S, Me ₂ S _g and target any combination thereof, and optionally additionally sulfur and / or H ₂ S, and the reaction mozh to be carried out in a closed vessel in the absence of air.

In the preparation of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, additives can be added to the reaction mixture before, during and upon completion of the reaction.

These additives can be H ₂ S, (alkali metal ion) H ₂ PO ₄ , (alkali metal ion) ₂ HPO ₄ , (alkali metal ion) ₃ PO ₄ , (alkali metal ion) HCO ₃ , (alkali metal ion) ₂ CO ₃ , (alkali metal ion) ₂ SO ₄ and (alkali metal ion) HSO ₄ .

In the preparation of organosilanes of the general formula I, where X is S, and m is from 1.5 to 4.5, in a preferred embodiment, the reaction can be carried out in a closed vessel.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, the reaction can be carried out under increased pressure from> 0.1 to <20, preferably from> 0.1 to <15, particularly preferably from> 0.5 to <10, most preferably from> 0.5 to <6 bar. In the preparation of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, in a preferred embodiment, the reaction can be carried out in the absence of air.

In the preparation of organosilanes of the general formula I, where X is S and a m is from 1.5 to 4.5, in a preferred embodiment, the reaction can be carried out in such a way that the gas formed cannot escape from the reaction space.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, the amount of alcohol can be at least 5, preferably from 10 to 300, particularly preferably from 10 to 200, particularly preferably from 10 to 150 vol.% In terms of the used silane components. The ethanol used may contain water.

In this third embodiment, the organosilanes of general formula I can be mixtures of organosilanes of general formula I having an average sulfur chain length, i.e. m, component from 1.5 to 4.5, and these organosilanes may have sulfur chains from S1 to S12, for example in the case of [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S _m :

[(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S, [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₂ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₃ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₄ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₅ , [(MeO) ₃ Si (CH _{2) 3] 2} S _6, [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₇ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₈ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₉ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₀ ,

[(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₁ , [(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₂ ,

in the case of [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S _m :

[(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S, [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₂ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₃ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₄ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₅ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₆ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₇ , [(EtO) ₃ Si (CH _{2) 3] 2} S _8, [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₉ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₀ ,

[(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₁ , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₂

in the case of [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S _m :

[(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₂ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₃ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₄ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₅ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₆ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₇ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₈ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₉ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₀ ,

[(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₁ , [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S ₁₂ .

Organosilanes of the general formula I may be:

[(MeO) ₃ Si (CH ₂ ) ₃ ] ₂ S _m , [(EtO) ₃ Si (CH ₂ ) ₃ ] ₂ S _m [(C ₃ H ₇ O) ₃ Si (CH ₂ ) ₃ ] ₂ S _m ,

[(C ₁₂ H ₂₅ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₂ H ₂₅ O) ₃ ],

[(C ₁₄ H ₂₉ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₄ H ₂₉ O) ₃ ],

[(C ₁₆ H ₃₃ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₆ H ₃₃ O) ₃ ],

[(C ₁₈ H ₃₇ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₈ H ₃₇ O ₃ )],

[(C ₁₂ H ₂₅ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₄ H ₂₉ O) ₃ ],

[(C ₁₄ H ₂₉ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₆ H ₃₃ O) ₃ ],

[(C ₁₆ H ₃₃ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₈ H ₃₇ O) ₃ ],

[(C ₁₈ H ₃₇ O) ₃ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (C ₁₄ H ₂₉ O) ₃ ],

[(C ₁₂ H ₂₅ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) ₂ ],

[(C ₁₂ H ₂₅ O) (C ₁₄ H ₂₉ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) (C ₁₄ H ₂₉ O)],

[(C ₁₂ H ₂₅ O) (C ₁₄ H ₂₉ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) (C ₁₂ H ₂₅ O)],

[(C ₁₂ H ₂₅ O) (C ₁₆ H ₃₃ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) (C ₁₆ H ₃₃ O)],

[(C ₁₂ H ₂₅ O) (C ₁₈ H ₃₇ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₂ H ₂₅ O) (C ₁₈ H ₃₇ O)],

[(C ₁₂ H ₂₅ O) (C ₁₈ H ₃₇ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₈ H ₃₇ O) ₂ ],

[(C ₁₄ H ₂₉ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₄ H ₂₉ O) ₂ ],

[(C ₁₄ H ₂₉ O) (C ₁₆ H ₃₃ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₄ H ₂₉ O) (C ₁₆ H ₃₃ O)],

[(C ₁₄ H ₂₉ O) (C ₁₈ H ₃₇ O) (CH ₃ ) Si (CH ₂ ) ₃ S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₄ H ₂₉ O) (C ₁₈ H ₃₇ O)],

[(C ₁₆ H ₃₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₆ H ₃₃ O) ₂ ],

[(C ₁₆ H ₃₃ O) (C ₁₈ H ₃₇ O) (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₆ H ₃₃ O) (C ₁₈ H ₃₇ O)],

[(C ₁₈ H ₃₇ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) (C ₁₈ H ₃₇ O) ₂ ],

[(C ₁₂ H ₂₅ O) (CH _{3) 2} Si (CH _{2) 3]} S _m [(CH _{2) 3} Si (CH _{3) 2} (C ₁₂ H ₂₅ O)],

[(C ₁₂ H ₂₅ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₄ H ₂₉ O)],

[(C ₁₂ H ₂₅ O) (CH _{3) 2} Si (CH _{2) 3]} S _m [(CH _{2) 3} Si (CH _{3) 2} (C ₁₆ H ₃₃ O)]

[(C ₁₂ H ₂₅ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₈ H ₃₇ O)],

[(C ₁₄ H ₂₉ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₄ H ₂₉ O)],

[(C ₁₄ H ₂₉ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₆ H ₃₃ O)],

[(C ₁₄ H ₂₉ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₈ H ₃₇ O)],

[(C ₁₆ H ₃₃ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₆ H ₃₃ O)],

[(C ₁₆ H ₃₃ O) (CH ₃ ) ₂ Si (CH ₂ ) ₃ ] S _m [(CH ₂ ) ₃ Si (CH ₃ ) ₂ (C ₁₈ H ₃₇ O)],

[(C ₁₈ H ₃₇ O) (CH _{3) 2} Si (CH _{2) 3]} S _m [(CH _{2) 3} Si (CH _{3) 2} (C ₁₈ H ₃₇ O)],

where m is from 1.5 to 4.5.

The compounds of General formula I, where X is S and m is from 1.5 to 4.5,

in a preferred embodiment, can be obtained by the reaction of aqueous sulfonating reagents with (haloorgan) alkoxysilanes of General formula II

in alcohol in a closed vessel in the absence of air and under increased pressure in the presence of additives.

In the preparation of organosilanes of the general formula I, where X is S and m is 1.5 to 4.5, the additives can be, for example, organic or inorganic acids, or organic or inorganic bases.

Organic acids can be compounds of the following starting configurations: alkyl-COOH, aryl-COOH, aralkyl-COOH, alkyl-S (O) ₂ OH, HOOC-alkylene-COOH, HOOC-aryl-COOH or HOOC-aralkyl-COOH.

Organic acids can be, for example, formic acid, acetic acid, propanoic acid, pivalic acid, isooctanoic acid, isononanoic acid, lauric acid (C12), myristic acid (C14), palmitic acid (C16), stearic acid (C18), oleic acid, linoleic acid, linolenic acid, benzoic acid, oxalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, 1,12-dodecanoic acid, aminoundecanoic acid, phthalic acid, terephthalic acid, maleic acid, fumar Wai acid, malonic acid, acrylic acid and methacrylic acid.

Inorganic acids can be, for example, compounds of the composition HCl, H ₂ SO ₄ , H ₃ PO ₄ , (alkali metal ion) H ₂ PO ₄ , (alkali metal ion) ₂ HPO ₄ , H ₃ CO ₃ , (alkali metal ion) HCO ₃ or (alkali metal ion) HSO ₄ .

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, acidic or basic additives that are introduced into the reaction mixture before, during or at the end of the process may have a structure (alkali metal ion) H ₂ PO ₄ , (alkali metal ion) ₂ HPO ₄ , (alkali metal ion) ₃ PO ₄ , (alkali metal ion) HCO ₃ , (alkali metal ion) ₂ CO ₃ , (alkali metal ion) ₂ SO ₄ or ( alkali metal ion) HSO ₄ .

In the preparation of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, haloorgan (halosilanes) can be used as additives.

In the preparation of organosilanes of the general formula I, where X is S, and m is from 1.5 to 4.5, compounds of the general formula III can be used as (haloorgan) halosilanes

in which Hal, R and R ″ have the above meanings, and R ″ ″ are independently R or Hal.

In the preparation of organosilanes of the general formula I, where X is S, and m is from 1.5 to 4.5, (chloroorgan) halosilanes may preferably be (chloroorgan) chlorosilanes.

In the preparation of organosilanes of the general formula I, where X is S and a m is from 1.5 to 4.5, the above compounds can be preferably used as (haloorgan) halosilanes.

In the preparation of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, the (haloorgan) halosilane may be a (haloorgan) halosilane of the general formula III or a mixture of (haloorganyl) chlorosilanes of the general formula III.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, as additives before and / or during and / or upon completion of the reaction, in combination with alcohols, compounds which release inorganic compounds can be introduced or organic acids.

Chlorosilanes can serve as compounds that release inorganic acids in the presence of alcohols. Chlorosilanes can contain from 1 to 4 Si-Cl bonds per silicon atom. Chlorosilanes can be (CH ₃ ) SiCl ₃ , (CH ₃ ) ₂ SiCl ₂ , (CH ₃ ) ₃ SiCl, SiCl ₄ , HSiCl ₃ , H ₂ SiCl ₂ .

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, compounds which release organic or inorganic bases in combination with alcohols can be administered as additives before and / or during, and / or upon completion of the reaction.

Compounds of General formula I, where X is S, a m is from 1.5 to 4.5,

in a preferred embodiment, can be obtained by the reaction of aqueous sulfonating reagents with (haloorgan) alkoxysilanes of General formula II

in alcohol in a closed vessel in the absence of air and under high pressure in the presence of H ₂ S.

The amount of H ₂ S in the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, can be less than 500, preferably less than 100, particularly preferably less than 50, even more preferably less than 15 mol% in terms of the amount of halogenorgan (alkoxysilane) used.

In the preparation of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, the crude product yield of the process according to the invention can be greater than 80, preferably greater than 85, particularly preferably greater than 90, even more preferably more than 95% in terms of theoretical yield and relative to the combination of (haloorgan) alkoxysilane and (haloorgan) halosilane.

In the preparation of organosilanes of the general formula I, where X is S and a m is from 1.5 to 4.5, the yield of the crude product can be determined gravimetrically as the sum of all the liquid compounds isolated after the solvent and solid particles are removed.

In the preparation of organosilanes of general formula I, where X is S, am is from 1.5 to 4.5, the composition of compounds or mixtures of compounds of general formula I, where X is S, am is from 1.5 to 4.5, can to influence the active and targeted way by choosing the composition of the mixtures (haloorgan) alkoxysilanes used, sulfonating reagents and alcohol, the amount of alcohol and additives.

A mixture of the corresponding (haloorgan) alkoxysilane and additives used in the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, can be obtained before the addition of sulfonating reagents, depending on the device used and the desired effects, some of which can be influenced independently of each other, for example, the selectivity of the reaction, the duration of the reaction, the productivity of the reactor, the reaction of (haloorgan) alkoxysilane and a sulfonating reagent with each other, the value of m in condition X boznachaet S _m, the reaction of an alkali metal sulfide and sulfur, the reaction of an alkali metal hydrosulfide and sulfur, the reaction of an alkali metal hydrosulfide, an alkali metal sulfide and sulfur, the reaction material or process sequence.

A mixture of the corresponding sulfonating reagents, sulfur and additives used in the preparation of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, can be prepared before the addition of haloorgan (alkoxysilane), depending on the device used and target effects, some of which can be influenced independently of each other, reactor material or process sequence.

The quality and type of composition of the mixture (haloorgan) of alkoxysilane and additives used in the preparation of organosilanes of general formula I, where X is S and m is from 1.5 to 4.5, can be estimated based on the amount and type of Si- hydrolyzable halide bonds contained in this mixture.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, the amount of Si halide capable of hydrolyzing in the above-mentioned mixtures of (haloorgan) alkoxysilane and additives, which can be determined by the above analysis method, can be within from 2 to 800,000, preferably in the range of 10 to 80,000, particularly preferably in the range of 10 to 40,000, most preferably in the range of 100 to 10,000 mg / kg.

The amount of hydrolyzable halide in mixtures of haloorgan (alkoxysilane) and additives used in the preparation of organosilanes of general formula I, where X is S, am is from 1.5 to 4.5, is determined according to the following method: in a 150-milliliter beaker not more than 20 g of the sample add 80 ml of ethanol and 10 ml of acetic acid. The halide content is determined by potentiographic titration with a solution of silver nitrate (at a concentration of (AgNO ₃ ) of 0.01 mol / l).

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, the preferred molar ratios of mixtures of (haloorgan) alkoxysilanes and (haloorgan) halosilanes (the additive is (haloorgan) halosilane) may depend, in addition to among other things, from the number of Si-halide functional groups of selected (haloorgan) halosilanes.

For example, in the reaction of 3-chloropropyl (trimethoxysilane) or 3-chloropropyl (triethoxysilane) and 3-chloropropyl (trichlorosilane), a molar ratio of from 1: 0.00001 to 1: 0.03 can be used in a preferred embodiment.

Thus, for example, in the reaction of 3-chloropropyl (methyldimethoxysilane) or 3-chloropropyl (methyldiethoxysilane) and 3-chloropropyl (methyldichlorosilane), a molar ratio of from 1: 0.00001 to 1: 0.045 can be preferably used.

For example, in the reaction of 3-chloropropyl (dimethylmethoxysilane) or 3-chloropropyl (dimethylethoxysilane) and 3-chloropropyl (dimethylchlorosilane), a molar ratio of from 1: 0.00001 to 1: 0.09 can be used in a preferred embodiment.

In the preparation of organosilanes of the general formula I, where X is S and m is 1.5 to 4.5, (haloorgan) alkoxysilane and the additives can be mixed together in any desired sequence or by any means at any target temperature and any desired duration , and only then alcohol and sulfonating reagents are added simultaneously or sequentially.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, additives, sulfonating reagents and alcohol can be mixed together in any desired sequence or by any means at any target temperature and at any desired duration and only then (haloorganyl) alkoxysilane is added.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, (haloorgan) alkoxysilane, sulfonating agents and alcohol can be mixed together in any desired sequence or by any means at any target temperature and at any necessary duration, and only after that add additives.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, (haloorgan) alkoxysilane, sulfonating agents and additives can be mixed together in any desired sequence or by any means at any target temperature and at any necessary duration, and only after that add alcohol.

Upon receipt of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, sulfonating reagents and additives can be mixed with each other in any desired sequence or by any means at any target temperature and at any desired duration, and only then alcohol and (haloorgan) alkoxysilane are added simultaneously or sequentially.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, water-containing sulfonating reagents that can be used are lithium hydrosulfide (LiSH), sodium hydrosulfide (NaSH), potassium hydrosulfide (KSH) or cesium hydrosulfide (CsSH).

Sulfurizing reagents, which in a preferred embodiment, can be used, are sodium and potassium sulfurizing reagents. In a particularly preferred embodiment, Na ₂ S, Na ₂ S ₂ , Na ₂ S ₃ , Na ₂ S ₄ , Na ₂ S ₅ , K ₂ S, K ₂ S ₂ , K ₂ S ₃ , K ₂ S ₄ or K ₂ S ₅ .

Water-containing sulfonating reagents can be added to the reaction mixture independently of each other before and / or during the reaction.

Water-containing sulfonating reagents can be independently mixed with sulfur or H ₂ S and added to the reaction mixture before, during or upon completion of the reaction.

In this third embodiment, the alkali metal hydrosulfide may include more than 3, preferably more than 5, particularly preferably more than 10, even more preferably more than 12, most preferably more than 15 wt.% Water.

In this third embodiment, Me ₂ S may include more than 10, preferably more than 15, particularly preferably more than 20, even more preferably more than 30 wt.% Water.

In this third embodiment, Me ₂ S _g may include more than 10, preferably more than 15, particularly preferably more than 20, even more preferably more than 30 wt.% Water.

Water-containing sulfonating reagents used in the preparation of organosilanes of the general formula I, where X is S and a is 1.5 to 4.5, can be introduced into the reaction in the form of solid particles or in solution.

The water-containing sulfonating reagents necessary for the reaction in the preparation of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, can be obtained from sulfur-containing compounds before or during the reaction.

Sulfur-containing compounds from which sulfonating reagents are prepared prior to or during the reaction in the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, can be H ₂ S, alkali metal sulfides Me ₂ S or alkali metal polysulfides Me ₂ S _g , preferably Li ₂ S, Na ₂ S, K ₂ S, Na ₂ S ₂ , Na ₂ S ₃ , Na ₂ S ₄ , K ₂ S ₂ , K ₂ S ₃ or K ₂ S ₄ .

Sulfur-containing compounds from which sulfonating reagents are obtained before or during the reaction can interact completely or not completely, reversibly or irreversibly due to protonation or deprotonation to form sulfonating reagents in the preparation of organosilanes of general formula I, where X is S, am is from 1.5 up to 4.5.

In the preparation of organosilanes of the general formula I, where X is S and a m is from 1.5 to 4.5, protonation or deprotonation of sulfur compounds from which alkali metal hydrosulfides are prepared before or during the reaction can be carried out using additives.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, raw materials that contain more than 40, preferably more than 50, particularly preferably more than 60, and most preferably more than 70 wt.% Alkaline hydrosulfide metal or which contain more than 30, preferably more than 40, particularly preferably more than 50, and most preferably more than 59 wt.% Me ₂ S, or which contain more than 20, preferably more than 30, particularly preferably more than 40, most preferably more than 50 wt.% Me ₂ S _g, not The dependence of each other may be used for preparing the reaction products of an alkali metal hydrosulfide, Me ₂ S, Me ₂ S _x and sulfur.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, water-containing sulfonating reagents may include, in addition to water, other secondary components in an amount of less than 50, preferably less than 30, particularly preferably less than 20 , even more preferably less than 10 wt.%.

In the preparation of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, the additional secondary components of the aqueous sulfonating reagents can independently be, in addition to water, alkali metal carbonates, alkali metal bicarbonates , alkali metal hydroxides, alkali metal sulfates, alkali metal bisulfates, alkali metal thiosulfates and / or alkali metal thiosulfates.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, the molar amount of the sulfonating reagent used may exceed the total molar amount of the used (haloorgan) alkoxysilane by 1 to 50, preferably by 1 up to 30, particularly preferably between 5 and 15 mol%.

In the preparation of organosilanes of the general formula I, where X is S, and m is from 1.5 to 4.5, the amounts of the sulfonating reagent of which are less than the stoichiometrically necessary amounts, can lead to incomplete conversion. Therefore, either the product is further contaminated with the starting material, or complex processing is required in order to separate the starting materials and products from each other.

The reaction temperature, which in each case is optimal, taking into account the yield of the target product and the use of the reaction volume, can be varied taking into account the type and amount, depending on the structure of the used (haloorgan) alkoxysilane and alcohol used as a solvent.

So, for example, in the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, preferred, taking into account the duration of the reaction, the amount of by-products and the pressure created in cases of reactions in methanol, can be a reaction a temperature in the range of 40 to 95, preferably in the range of 60 to 95 ° C.

So, for example, in the preparation of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, preferred, taking into account the duration of the reaction, the amount of by-products and the pressure created in cases of reactions in ethanol, may be reaction temperature in the range from 50 to 130, preferably in the range from 75 to 130 ° C.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, the reaction vessel, which is known in the art and makes it possible to carry out the process under pressures of up to 20 bar, can be used as a closed container at temperatures up to 200 ° C. The closed container may have a circulation means for heating / cooling.

In the preparation of organosilanes of the general formula I, where X is S and a m is from 1.5 to 4.5, the amount of by-product due to the choice of reaction conditions can be less than 20, preferably less than 15, particularly preferably less than 10 mol%.

In the preparation of organosilanes of the general formula I, where X is S and a m is from 1.5 to 4.5, the amount of by-product due to the choice of reaction conditions can be less than 20, preferably less than 15, particularly preferably less than 10 wt.%.

In the preparation of organosilanes of the general formula I, where X is S, am is from 1.5 to 4.5, the amount of residual haloorgan (alkoxysilane) starting material due to the choice of reaction conditions can be less than 20, preferably less than 15, especially preferably less than 10, still more preferably less than 5 wt.%.

In this third embodiment, the solvent / water mixture can be removed from the crude product suspension, preferably under reduced pressure, and the resulting suspension containing the organosilane of general formula I that is formed can be separated from the solid material, preferably by centrifugation, decantation or filtration.

The solvent / water mixture can be removed under pressure from 800 to 10 mbar, preferably by distillation. The solvent / water mixture may contain ethanol.

The resulting suspension may include Me (Hal), for example NaCl, buffer salts and organosilanes of the general formula I.

The solvent may be removed from the crude product suspension, the mixture comprising organosilanes of the general formula (I) and solid Me (Hal) may be mixed with water containing at least one buffer, and the phases formed may be separated.

Processing a slurry of a crude product may include filtering and removing solid components. Processing a suspension of the crude product may include distillation and removal of volatile components. Such processing of a slurry of a crude product may include first distillation and then filtration. Processing the suspension of the crude product may include first filtration and then distillation. Processing the suspension of the crude product may include first filtering, then distillation, and then further filtering.

The salt-containing suspension of the crude product present after the reaction can be treated under atmospheric pressure or reduced pressure, preferably under reduced pressure in the range from 1 to 700, particularly preferably in the range from 5 to 500, even more preferably in the range from 10 to 250 mbar .

The salt-containing suspension of the crude product contained after the reaction can be treated at room temperature or elevated temperature, preferably in the range of 20 to 200, particularly preferably in the range of 40 to 150, most preferably in the range of 50 to 100 ° C.

During processing, a mixture of product and solid material may form. During processing, a mixture of product and alcohol may form.

During processing, a mixture of product, alcohol and water may form. During processing, a mixture of product and water may form. During processing, a mixture of product, solid material and water may form. During processing, a mixture of the product, Me (Hal), for example sodium chloride, and water can form. During processing, a mixture of the product, Me (Hal), for example sodium chloride, alcohol and water, may form.

Water may be added to the mixture of the product and / or solid material and / or alcohol and / or water.

Water can be added in an amount of from 1 to 200, preferably from 1 to 100, particularly preferably from 5 to 75, even more preferably from 5 to 50 wt.% In terms of product.

Water may be demineralized water. Water may include a buffer, for example sodium bicarbonate or sodium carbonate. The buffer content in the water may be from 1 to 20, preferably from 2 to 5 wt.%.

The added water may have a pH in the range of 3 to 11, preferably in the range of 4 to 10, particularly preferably in the range of 5 to 9, even more preferably in the range of 7 to 9.

The pH of the added water can be adjusted with a buffer, for example NaHCO ₃ .

In a preferred embodiment, a solid material may be contained in the aqueous phase. In a preferred embodiment, the Me phase may contain a salt of Me (Hal), for example sodium chloride.

The product can be isolated from the phase-containing aqueous phase salt. After phase separation, the product can be isolated from the salt-containing aqueous phase. After isolation from the salt phase, the product can be dried.

The method in accordance with the invention has the advantage that, as its sulfonating reagents, it is possible to use easily metered solid particles, for example, aqueous sodium hydrogen sulfide or sodium sulfide, as its sulfonating reagents.

Moreover, the method in accordance with the invention has the advantage that it is possible to use commercially available, conventional aqueous sulphurization raw materials. These water-containing raw materials, which are not specially prepared, have an advantage over alkali metal hydrosulfides dried according to a complicated method (for example, dried to <3 wt.%).

One advantage is the reduced or even in the absence of spontaneous flammability of the raw materials for sulfonation due to the presence of an aqueous component. Therefore, they can be relatively safely divided into portions, transferred and handled in air. This saves the costs associated with additional efforts and technical systems in installations and safety devices. The danger to the technical operator is reduced due to the absence of a smoldering fire caused by the loss of alkali metal hydrosulfide or alkali metal sulfide Me ₂ S and the occurrence of smoke during its oxidation in air.

Another advantage is the simplification of the process and the improved energy balance of the process as a whole, if the sulfurizable raw materials should not be dried under vacuum at elevated temperatures or obtained from alkali metal and sulfur under severe reaction conditions.

The advantage over the azeotropic drying of sulfurizable raw materials is to simplify the process by eliminating the process step and eliminating the additional use, consumption or treatment of a solvent that acts as an aqueous azeotropic agent (azeotrope forming substance).

Another advantage of the method in accordance with the invention is that the selectivity, conversion and yield of the crude product can be increased by the simple use of a closed reaction vessel (autoclave or the like) and the introduction of small amounts of additives.

The high degree of conversion for short periods of time of the batch process and at temperatures that are technically easy to reach, is another advantage of the method in accordance with the invention.

The high yield of crude liquid products that do not precondensate to produce polysiloxanes is another advantage of the process of the invention. The method in accordance with the invention is characterized by a high yield of crude liquid products in combination with a high selectivity of the sulfurization reaction, for example, in the preparation of mercapto compounds of the general formula I, where X is SH, or polysulfide compounds of the general formula I, where X is S, am is a number from 1, 5 to 4.5.

The high content of monomer products determined by ²⁹ Si-NMR analysis is an additional advantage of the method in accordance with the invention. It should be assumed that the content of dimers and trimers is high in combination with a low yield of crude product as a result of hydrolysis of Si-O (alkyl) groups followed by condensation of the resulting silanol groups.

Examples

In the preparation of organosilanes, NaSH from ICS Wolfen GmbH, including from 25 to 35 wt.% Water, NaSH from Lanxi Darning Chem., Including from 15 to 25 wt.% Water, or NaSH from Goldschmldt TIB GmbH, including from 20 to 30 wt. .% water.

In the preparation of organosilanes, Tessenderlo's Na ₂ S can be used, comprising from 35 to 45 wt.% Water, Na ₂ S · XH ₂ O, which can be obtained, for example, from Aldrich or Merck-Schuchard, having a Na ₂ S content of 20 to 40 wt.%, Or Na ₂ S · 3H ₂ O, which can be obtained, for example, from Aldrich or Merck-Schuchard.

To evaluate the reaction mixtures, the degree of conversion is determined as the quotient of the percentage in the area of 3-mercaptopropyl (triethoxysilane), (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ and (EtO ) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃

and

the combination of percentages by area of 3-chloropropyl (triethoxysilane), 3-mercaptopropyl (triethoxysilane), siloxane dimers of 3-mercaptopropyl (triethoxysilane) and 3-chloropropyl (triethoxysilane),

(EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ and

(EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ .

To evaluate the reaction mixtures, selectivity is defined as the quotient as a percentage in the area of 3-mercaptopropyl (triethoxysilane)

and

the combination of percentages by area of 3-mercaptopropyl (triethoxysilane), siloxane dimers of 3-mercaptopropyl (triethoxysilane) and 3-chloropropyl (triethoxysilane),

(EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ and

(EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ .

To evaluate the reaction mixtures, the concentration of the crude product by GC is defined as the quotient as a percentage in the area of 3-mercaptopropyl (triethoxysilane)

and

fraction in percent by area for ethanol (solvent).

Analysis

GC analysis

GC analysis of the reaction mixtures was carried out in an HP 6890 gas chromatograph (WLD) equipped with a DB5 column 30 m long with an inner diameter of 0.53 mm and a film thickness of 1.5 μm. The used detector is a thermoconductometric detector. The temperature program used includes the following sequences:

initial temperature: 100 ° C

initial time: 1 min.

20 ° C / min to 280 ° C

exposure at 280 ° C: for 10 minutes

The retention time for the following components is:

within 3.3 minutes for Cl- (CH ₂ ) ₃ -Si (OEt) ₃

within 5.7 minutes for HS- (CH ₂ ) ₃ -Si (OEt) ₃

for 9.0-10.5 min for various siloxane dimers from the starting silane material and silane product

within 11.0 min for

(EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃

for 12.4 min for

(EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃

GC analysis of the isolated crude products is carried out in a gas chromatograph with PID using dodecane or toluene as the internal standard.

The gas chromatographic studies in Examples 5 to 11 are carried out as described in the Standard Test Method for Silanes Used in Rubber Formulatios (Bis (triethoxysilylpropyl) sulphanes): Characterization by Gas Chromatography (GC), D 6843-02.

HPLC analysis

A method for HPLC determination is described in "Luginsland, H-D., Reactivity of the Sulfur Functions of the Disulfane Silane TESPD and Tetraulfane Silane TESPT, paper presented at ACS Meeting, April 1999, Chicago."

The average length of the sulfur chain is calculated as follows:

обозначает среднюю длину серной цепи

denotes the average length of the sulfur chain

i denotes the number of sulfur atoms in the silane component

M _i denotes the molecular weight of the silane component with i sulfur atoms

A _i denotes the signal area of the silane component with i sulfur atoms

R _i denotes the coefficient of characteristics of the sulfur-containing silane component with i sulfur atoms

If the organosilanes of formula I, where X is S, contain compounds with S ₁ , then the average length of the sulfur chain is adjusted, taking into account the molecular weights.

²⁹ Si-NMR

Si spectra were recorded on a Bruker Avance 500-NMR spectrometer with a detection frequency of 99.35 MHz for Si (500.13 MHz H-NMR). These spectra are correlated with tetramethylsilane (TMS = 0 ppm) as an internal standard. To determine the samples used in the form approx. 30% solution in CDCl ₃ with the addition of chromium acetylacetonate (from about 0.05 to 0.1 molar solution) as a relaxation accelerator. Use a pulse frequency with decoupling from protons only during the time of perception and a 5-second relaxation delay.

Data ²⁹ Si-NMR ppm Attribution -46 R-Si (OR ') ₃ -53 R-Si (OR ') _2- O-Si -62 Si-O-Si (R) (OR ') - O-Si

Integral Correction

The trimer corresponds to the integral (-62 ppm)

The dimer corresponds to the integral (-53 ppm) - 2; the integral (-63 ppm) / 2

The monomer corresponds to (integral (-46 ppm) - 3 · integral (-62 ppm) - 2 · integral (-53 ppm) - 2 · integral (-62 ppm) / 2 ) / 2

The adjusted integrals are directly proportional to the mole fractions of the monomers, dimers, and trimers in the sample.

Example 1 (X is SH)

50 g of NaSH (70% strength with 25 wt.% Water) and 750 ml of ethanol at room temperature are first introduced into a four-necked flask, which can be heated using an oil bath, and stirred for 15 min at 50 ° C. 150 g of 3-chloropropyl (triethoxysilane) and an additional 150 ml of ethanol are added to the suspension. The mixture is heated with stirring and refluxed for 180 minutes. Then the mixture is cooled to about 55 ° C and 1 g of formic acid is metered into it. After 15 minutes, a sample was taken and analyzed by gas chromatography.

GC analysis of the reaction mixture gives the following composition in percent by area:

Ethanol 96,424 3-chloropropyl (triethoxysilane) 0,086 3-mercaptopropyl (triethoxysilane) 1,828 Siloxane dimers from silane as a starting material and silane product 0.322 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ 0.322 (EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ 0

Based on the above values, the conversion is> 96%, and the selectivity of the reaction is 74%. Based on the above values, the concentration of the crude product by GC is 1.9%.

The resulting suspension is filtered. The isolated filtrate is freed from volatile components in a rotary evaporator at a pressure of from 20 to 600 mbar and at a temperature of from 60 to 80 ° C. 47.4 g of a colorless insoluble solid are obtained.

Example 2 (X is SH)

60.9 g of NaSH (70% strength with 25 wt.% Water) and 750 ml of ethanol at room temperature are first introduced into a four-necked flask, which can be heated using an oil bath, and stirred for 15 min at 50 ° C. Using a burette, a mixture of 7.5 g of 3-chloropropyl (trichlorosilane) and 150 g of 3-chloropropyl (triethoxysilane) is added under pressure. An additional 150 ml of ethanol is added to the suspension. The mixture is heated with stirring and refluxed for 180 minutes. Then the mixture is cooled to about 55 ° C and 1 g of formic acid is metered into it. After 15 minutes, a sample was taken and analyzed by gas chromatography. GC analysis of the reaction mixture gives the following composition in percent by area:

Ethanol 97,973 3-chloropropyl (triethoxysilane) 0,021 3-mercaptopropyl (triethoxysilane) 1,042 Siloxane dimers from silane as a starting material and silane product 0.133 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ 0.142 (EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ 0.009

Based on the above values, the conversion is> 98%, and the selectivity of the reaction is 79%. Based on the above values, the concentration of the crude product by GC is 1.1%.

The resulting suspension is filtered. The isolated filtrate is freed from volatile components in a rotary evaporator at a pressure of from 20 to 600 mbar and at a temperature of from 60 to 80 ° C. 40 g of a colorless insoluble, highly viscous product are obtained.

Example 3 (X is SH)

50 g of NaSH (70% strength with 25 wt.% Water) and 750 ml of ethanol at room temperature are first introduced into an autoclave equipped with a glass double jacket and a cover made of Hastelloy C22 alloy + fittings (Buechi AG), and mixed for 15 min at 50 ° C. Using a burette, 150 g of 3-chloropropyl (triethoxysilane) are added under pressure. An additional 150 ml of ethanol is added to the suspension. The mixture with stirring is heated to a temperature of from 105 to 110 ° C and the temperature is maintained for 180 minutes. Then the mixture is cooled to approximately 55 ° C and 1 g of formic acid is metered into it. After 15 minutes, a sample was taken and analyzed by gas chromatography. GC analysis of the reaction mixture gives the following composition in percent by area:

Ethanol 91,611 3-chloropropyl (triethoxysilane) 0.195 3-mercaptopropyl (triethoxysilane) 5,659 Siloxane dimers from silane as a starting material and silane product 0.829 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ 0.253 (EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ 0,033

Based on the above values, the conversion is> 97%, and the selectivity of the reaction is 84%. Based on the above values, the concentration of the crude product by GC is 6.2%.

The resulting suspension is filtered. The isolated filtrate is freed from volatile components in a rotary evaporator at a pressure of from 20 to 600 mbar and at a temperature of from 60 to 80 ° C. The precipitated solid is separated by filtration. 85.2 g of a colorless liquid are obtained. The yield of crude product is 57.4%.

Analysis by gas chromatography (dodecan as an internal standard) gives the following composition of the obtained crude product in mass percent (wt.%):

3-Chlorpropyl (triethoxysilane) (GC) 1.8 3-Mercaptopropyl (triethoxysilane) (GC) 52,2 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ (GC) 2.2

Example 4 (X is SH)

60.9 g of NaSH (70% strength with 25 wt.% Water) and 750 ml of ethanol at room temperature are first introduced into an autoclave equipped with a glass double jacket and a cover made of Hastelloy C22 alloy + fittings (manufactured by Buechi AG), and stirred for 15 min at 50 ° C. Using a burette, a mixture of 7.5 g of 3-chloropropyl (trichlorosilane) and 150 g of 3-chloropropyl (triethoxysilane) is added under pressure. An additional 150 ml of ethanol is added to the suspension. The mixture is heated to a temperature of 105 to 110 ° C with stirring and the temperature is maintained for 180 minutes. Then the mixture is cooled to approximately 55 ° C and 1 g of formic acid is metered into it. After 15 minutes, a sample was taken and analyzed by gas chromatography. GC analysis of the reaction mixture gives the following composition in percent by area:

Ethanol 84,203 3-chloropropyl (triethoxysilane) 0,057 3-mercaptopropyl (triethoxysilane) 12,591 Siloxane dimers from silane as a starting material and silane product 0.349 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ 0.232 (EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ 0.179

Based on the above values, the conversion is> 99%, and the selectivity of the reaction is 94%. Based on the above values, the concentration of the crude product by GC is 14.9%.

The resulting suspension is filtered. The isolated filtrate is freed from volatile components in a rotary evaporator at a pressure of from 20 to 600 mbar and at a temperature of from 60 to 80 ° C. The precipitated solid is separated by filtration. 141.7 g of a colorless liquid are obtained. The yield of crude product is 90.3%. The resulting liquid has a residual water content of 0.3 wt.%.

Analysis by gas chromatography (dodecan as an internal standard) gives the following composition of the obtained crude product in mass percent (wt.%):

3-Chlorpropyl (triethoxysilane) (GC) 0.4 3-Mercaptopropyl (triethoxysilane) (GC) 77.6 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ (GC) 1,5

Example 5 (X is S, and m is 2.1)

Initially, 300 g of ethanol, 96.7 g of K ₂ CO ₃ , 33.6 g of NaHCO ₃ , 37.1 g of elemental sulfur and 63.3 g of NaSH hydrate (71% strength, contains 25 wt.% Water) at room temperature temperature is introduced into an autoclave equipped with a glass double jacket and a cover made of Hastelloy C22 alloy + fittings (manufactured by Buechi AG), and maintained at 80 ° C. After 30 minutes, 500 g of 3-chloropropyl (triethoxysilane) was slowly added. The pressure in the reactor increases to 3.5 bar. After 20 minutes, 13.15 g of Na ₂ S hydrate (with a water content of 36% by weight) was added. This addition is repeated 3 times, whereby the total amount of Na ₂ S hydrate is 52.6 g. After another 30 minutes, cooling is carried out and the salt is separated and washed with ethanol. The solvent is removed from the product under reduced pressure and at about 80 to 110 ° C.

A slightly yellow crude liquid product is obtained with a yield of 93%.

GC, HPLC and ²⁹ Si-NMR analyzes give the following values:

3-chloropropyl (triethoxysilane) / GC 2.9 wt.% 3-Mercaptopropyl (triethoxysilane) / GC 2.1 wt.% (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ / GC 0.1 wt.% The average length of the sulfur chain S _m / HPLC + GC 2.2 Monomer Content / ²⁹ Si-NMR 93.0 wt.%

Example 6 (S is X, and m is 2.7)

Initially, 300 g of ethanol, 37.0 g of elemental sulfur and 63.2 g of NaSH hydrate (71% strength, contains 25 wt.% Water) are introduced at room temperature into an autoclave equipped with a glass double jacket and a Hastella lid C22 + fittings (manufactured by Buechi AG), and maintained at 80 ° C. After 30 minutes, 500 g of 3-chloropropyl (triethoxysilane) was slowly added. The pressure in the reactor increases to 3.5 bar. After 20 minutes, 13.3 g of Na ₂ S hydrate (with a water content of 36% by weight) was added. This addition is repeated 3 times, resulting in a total of 53.2 g of Na ₂ S hydrate in the reaction mixture. After another 30 minutes, cooling is carried out and the salt is separated and washed with ethanol. The solvent is removed from the product under reduced pressure and at about 80 to 110 ° C.

A slightly yellow crude liquid product is obtained with a yield of 98%.

GC, HPLC and ²⁹ Si-NMR analyzes give the following values:

3-chloropropyl (triethoxysilane) / GC 14.6 wt.% 3-Mercaptopropyl (triethoxysilane) / GC 7.8 wt.% (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ / GC 0.1 wt.% The average length of the sulfur chain S _m / HPLC + GC 2.7 Monomer Content / ²⁹ Si-NMR 100 wt.%

Example 7 (X is S and m is 3.7)

Initially, 300 g of ethanol, 100.0 g of elemental sulfur and 33.7 g of NaSH hydrate (71% strength, contains 25 wt.% Water) together with 96.7 g of K ₂ CO ₃ and 33.6 g of NaHCO ₃ at room temperature is introduced into an autoclave equipped with a glass double jacket and a cover made of Hastelloy C22 alloy + fittings (manufactured by Buechi AG), and maintained at 80 ° C. After 30 minutes, 500 g of 3-chloropropyl (triethoxysilane) was slowly added. The pressure in the reactor increases to 3.5 bar. After 20 minutes, 17.6 g of Na ₂ S hydrate (with a water content of 36% by weight) was added. This addition is repeated 3 times, as a result of which a total of 70.4 g of Na ₂ S hydrate is contained in the reaction mixture. After another 30 minutes, cooling is carried out and the salt is separated and washed with ethanol. The solvent is removed from the product under reduced pressure and at about 80 to 110 ° C.

A red crude liquid product is obtained with a yield of 98%.

GC, HPLC and ²⁹ Si-NMR analyzes give the following values:

3-chloropropyl (triethoxysilane) / GC 3.4 wt.% 3-Mercaptopropyl (triethoxysilane) / GC 1.6 wt.% (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) 3 / GC 0.0 wt.% The average length of the sulfur chain / HPLC + GC 3,7 Monomer Content / ²⁹ Si-NMR 98 wt.%

Example 8 (X is S, and m is 2.67)

Initially, 251 g of ethanol, 18.6 g of elemental sulfur, 35.9 g of NaSH hydrate (71% strength, contains 25 wt.% Water), 48.5 g of K ₂ CO ₃ and 16.9 g of NaHCO ₃ at room temperature introduced into a 3-necked flask equipped with a stirrer, thermometer and reflux condenser, and kept at 80 ° C. After 30 minutes, 250 g of 3-chloropropyl (triethoxysilane) was slowly added. After 60 minutes, cooling was carried out and the salt was separated and washed with ethanol. The solvent is removed from the product under reduced pressure and at about 80 to 110 ° C.

A yellow crude liquid product is obtained with a yield of 98%.

¹ H- and ²⁹ Si-NMR analyzes give the following values:

3-chloropropyl (triethoxysilane) / GC 35.9 wt.% 3-Mercaptopropyl (triethoxysilane) / GC 0.0 wt.% (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ / GC 0.0 wt.% The average length of the sulfur chain S _m / HPLC 2.67 Monomer Content / ²⁹ Si-NMR 92.1 wt.%

Example 9 (X is S and m is 3.6)

Initially, 481 g (2 mol) of DYNASYLAN CPTEO product (CPTEO: 3-chloropropyltriethoxysilane from Degussa AG), 88 g (2.75 mol) of sulfur, 120 ml of ethanol, 5 g of NaHCO ₃ and 5 g of Na ₂ CO ₃ are charged and stirred. temperature from 65 to 70 ° C. 132 g (2 mol) of Na ₂ S · 3H ₂ O (Tessenderlo Chemie Belgium, water content of about 36 wt.%) Are added in 4 portions to this mass over one hour. After the addition of Na ₂ S · 3H ₂ O, which is previously finely ground, a slight increase in the reaction temperature is noted. The mass turns bright red.

One hour after the last portion of Na ₂ S · H ₂ O was added, a sample was first taken and examined by GC. The reaction mixture still contains 12.2% by weight of CPTEO product. After the next hour, the content of the CPTEO product decreases to 5.6 wt.% And to 3.2 wt.% After 3 hours. After the four-hour reaction time, the content of the CPTEO in the reaction mixture is still 2.1 wt.% (In total difficulty for GC analyzes, approximately 20 g of the reaction mixture was taken). After four hours, the reaction mixture has a yellow-orange color.

Ethanol and water are distilled off in a rotary evaporator (pressure from about 200 to <1 mbar, mass temperature: from 25 to 100 ° C). 130 g of distillate are obtained (with a water content of 37%, i.e. 48 g of water).

The salt is separated by filtration and washed twice with cyclohexane and once with ethanol.

After removal of the solvent, 497 g of a yellow product is obtained, characterized by the following analytical data:

3-chloropropyl (triethoxysilane) / GC 1.5 wt.% The average length of the sulfur chain S _m / HPLC 3.6 Monomer Content / ²⁹ Si-NMR 98.4 wt.%

Example 10 (X is S, and m is 3.73)

The following substances are first charged to a 1 liter reactor:

481 g (2 mol) of CPTEO product,

91 g (2.85 mol) of powdered sulfur,

120 ml of ethanol

5 g of NaHCO ₃ and

5 g of NaCO ₃ .

Then the contents of the reactor are heated to 50 ° C. Next, to the reaction mixture with stirring for _^1/2 h 4 is added in portions 132 g (2 moles) Na ₂ S · 3H ₂ O (finely ground, with a water content of about 36 wt.%). During this addition, a slight increase in temperature is detected in the reactor.

After the addition of Na ₂ S · 3H ₂ O was completed, the contents of the reactor were stirred for 3 hours at 68 ° C to complete the reaction.

GC analyzes of the reaction mixture indicate a CPTEO product content of 2.3%.

Without cooling, the reaction mixture was transferred to a rotary evaporator and ethanol and water were removed. At a pressure of 400 mbar and at a temperature of from 70 to 96 ° C, 80% of ethanol / water is distilled off. The remaining 20% ethanol / water is distilled off under pressure from 400 to 1 mbar and at a temperature of 96 ° C.

The Si 69 / NaCl mixture in the reactor was cooled to 50 ° C and then 330 ml of buffer demineralized water (2% NaHCO ₃ ) was added over 5 minutes to dissolve NaCl.

Immediately after turning off the agitator, phase separation occurs.

The water content in the organic phase (detectable slightly green color) is 2800 ppm.

After that, the organic phase is dried in a rotary evaporator (under a pressure of 1 mbar, at a temperature of 96 ° C) and then filtered. 488 g of a yellow product are obtained.

Analytical data by GC, HPLC and ²⁹ Si-NMR of the final product:

3-chloropropyl (triethoxysilane) / GC 1.7 wt.% The average length of the sulfur chain S _m / HPLC 3.73 Monomer Content / ²⁹ Si-NMR 94.1 wt.%

Example 11 (X is S, and m is 3.74)

The following substances are first charged to a 1 liter reactor:

481 g (2 mol) of CPTEO product,

91 g (2.85 mol) of powdered sulfur,

120 ml of azeotropic ethanol (95% ethanol, 5% water),

5 g of NaHCO ₃ ,

5 g of NaCO ₃ .

Then the contents of the reactor are heated to 50 ° C. Next, to the reaction mixture with stirring for _^1/2 h 4 is added in portions 132 g (2 moles) Na ₂ S · 3H ₂ O (finely ground, with a water content of about 36 wt.%). During this addition, a slight increase in temperature is detected in the reactor.

After the addition of Na ₂ S · 3H ₂ O was completed, the contents of the reactor were stirred for 3 hours at 68 ° C to complete the reaction.

GC analyzes of the reaction mixture indicate a CPTEO product content of 2.5%.

Then, without cooling, the reaction mixture was transferred to a rotary evaporator and ethanol and water were removed. At a pressure of 400 mbar and at a temperature of from 70 to 96 ° C, 80% of ethanol / water is distilled off. The remaining 20% ethanol / water is distilled off under pressure from 400 to 1 mbar and at a temperature of 96 ° C.

Next, the Si 69 / NaCl mixture in the reactor is cooled to 50 ° C, and then 330 ml of demineralized buffer water (2% NaHCO ₃ ) is added over 5 minutes to dissolve NaCl.

Immediately after turning off the agitator, phase separation occurs.

The water content in the organic phase (detectable slightly green color) is 2800 ppm.

After that, the organic phase is dried in a rotary evaporator (under a pressure of 1 mbar, at a temperature of 96 ° C) and then filtered. 489 g of a yellow product are obtained.

Analytical data by GC, HPLC and ²⁹ Si-NMR of the final product:

3-chloropropyl (triethoxysilane) / GC 2.0 wt.% The average length of the sulfur chain S _m / HPLC 3.74 Monomer Content / ²⁹ Si-NMR 91.0 wt.%

Example 12 (X is S, and m is 2.16)

Initially, at room temperature, 200 g of ethanol (containing 7.5% H ₂ O), 55.0 g of Na ₂ CO ₃ are charged into an autoclave equipped with a glass double jacket and a lid made of Hastelloy C22 + fittings (manufactured by Buechi AG) , 5.0 g of NaHCO ₃ , 25.0 g of Na ₂ S hydrate (61% strength, contains 37% H ₂ O), 26.4 g of elemental sulfur and 66.05 g of NaSH hydrate (71% strength) contains 29% H ₂ O) and is maintained at 68 ° C in a closed system. The pressure in the reactor increases. After 20 minutes, 3-chloropropyltriethoxysilane is slowly dosed so that the reaction temperature does not exceed 70 ° C. After dosing for 120 minutes, thermostating is carried out at 80 ° C. After this, cooling is carried out, the increased pressure is discarded and the salt is separated and washed with ethanol. The solvent is removed from the product under reduced pressure at about 70 ° C.

A slightly yellow crude product is obtained with a yield of 94%.

GC, HPLC and ²⁹ Si-NMR analyzes give the following values:

3-chloropropyl (triethoxysilane) / GC 1.9 wt.% 3-Mercaptopropyl (triethoxysilane) / GC 1.6 wt.% (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ / GC 0.3 wt.% The average length of the sulfur chain / HPLC + GC 2.16 Monomer Content / ²⁹ Si-NMR 100 wt.%

Example 13 (X is S, and m is 3.71)

Initially, at room temperature, 150 g of ethanol (containing 7.5% H ₂ O), 34.0 g of Na ₂ CO ₃ are charged into an autoclave equipped with a glass double jacket and a lid made of Hastelloy C22 + fittings (manufactured by Buechi AG) , 55.0 g of Na ₂ S hydrate (61% strength, contains 37% H ₂ O), 68.0 g of elemental sulfur and 25.75 g of NaSH hydrate (71% strength, contains 29% H ₂ O ) and maintained at 68 ° C in a closed system. The pressure in the reactor increases. After 20 minutes, 3-chloropropyltriethoxysilane is slowly dosed so that the reaction temperature does not exceed 70 ° C. After dosing for 120 minutes, thermostating is carried out at 74 ° C. After this, cooling is carried out, the increased pressure is discarded and the salt is separated and washed with ethanol. The solvent is removed from the product under reduced pressure at about 70 ° C.

A slightly yellow crude product is obtained with a yield of 94.5%.

GC, HPLC and ²⁹ Si-NMR analyzes give the following values:

3-Chloropropyl (triethoxysilane) / GC 2.5 wt.% 3-Mercaptopropyl (triethoxysilane) / GC 0.2 wt.% (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ / GC 0.1 wt.% The average length of the sulfur chain / HPLC + GC 3.71 Monomer Content / ²⁹ Si-NMR 97.2 wt.%

Example 14 (X is S, and m is 3.62)

Initially, at room temperature, 150 g of ethanol (containing 7.5% H ₂ O), 34.0 g of Na ₂ CO ₃ are charged into an autoclave equipped with a glass double jacket and a lid made of Hastelloy C22 + fittings (manufactured by Buechi AG) , 55.0 g of Na ₂ S hydrate (61% strength, contains 37% H ₂ O), 68.0 g of elemental sulfur and 25.75 g of NaSH hydrate (71% strength, contains 29% H ₂ O ) and maintained at 68 ° C in a closed system. The pressure in the reactor increases. After 20 minutes, 3-chloropropyltriethoxysilane is slowly dosed so that the reaction temperature does not exceed 70 ° C. After dosing for 120 minutes, thermostating is carried out at 74 ° C. After this, cooling is carried out, the increased pressure is discarded and the salt is separated and washed with ethanol. The solvent is removed from the product under reduced pressure at about 70 ° C.

A slightly yellow crude product is obtained with a yield of 94%.

GC, HPLC and ²⁹ Si-NMR analyzes give the following values:

3-Chlorpropyl (methyldiethoxysilane) / GC 4.0 wt.% The average length of the sulfur chain / HPLC + GC 3.62

Example 15 (X is SH)

Initially, at room temperature, 52 g of NaSH (70% strength with 25 wt.% Water) with 500 ml of ethanol (quality) are charged into an autoclave equipped with a glass double jacket and a Hastella C22 alloy cap + fittings (Buechi AG company) Seccosolv, not more than 0.02% water) and the autoclave is closed. The suspension is maintained at 55 ° C for 20 minutes. Using a pump, a mixture of 100 g of 3-chloropropyl (dimethylethoxysilane) and 5 g of 3-chloropropyl (dimethylchlorosilane) is metered into the suspension. Then an additional 300 ml of ethanol (Seccosolv quality, not more than 0.02% water) is added to this mixture by pump. The stirring mixture is heated to 93 ° C and the temperature is maintained for 180 minutes. Then the mixture is cooled and the autoclave is opened. The contents of the reactor are discharged and filtered. The filter cake is washed with toluene. GC analysis of the crude product gives the following components in% by area:

Ethanol 79.1 Toluene 15,5 3-chloropropyl (dimethylethoxysilane) 0.5 3-mercaptopropyl (dimethylethoxysilane) 3,5 Siloxane dimer 0,03 (EtO) ₃ Si- (CH ₂ ) ₃ -S _x - (CH ₂ ) ₃ -Si (OEt) ₃ 0.2

Based on the above values, the conversion is 88% and the selectivity of the reaction is 94%.

In a rotary evaporator, the filtrate is freed from the solvent. The residue is taken up with toluene and filtered. The filter cake is thoroughly washed with toluene and the filtrate is freed from the solvent in a rotary evaporator. 82.5 g of a liquid final product are obtained.

Example 16 (X is SH)

Initially, at room temperature, 59.4 g of NaSH (70% strength with 25 wt.% Water) with 500 ml of ethanol are charged into an autoclave equipped with a glass double jacket and a Hastella C22 alloy cap + fittings (manufactured by Buechi AG) and the autoclave is closed. The suspension is maintained at 50 ° C for 15 minutes. A mixture of 100 g of 3-chloropropyl (dimethylethoxysilane) and 15 g of 3-chloropropyl (dimethylchlorosilane) is metered into the suspension using a pump. Next, an additional 100 ml of ethanol is added to this mixture by pump. The mixture is heated to 95 ° C with stirring and the temperature is maintained for 150 minutes. Then the mixture is cooled and the autoclave is opened. The contents of the reactor are discharged, 1.4 g of formic acid are added, stirring is carried out for 15 minutes and then filtration is carried out. The filter cake was washed with ethanol and the filtrate was removed from the solvent in a rotary evaporator. 108.7 g of the liquid final product are isolated.

Example 17 (X is SH)

Initially, at room temperature, 180 g of NaSH (70% strength with 24 wt.% Water) with 300 g of ethanol and 25 g are loaded into an autoclave equipped with a glass double jacket and a Hastella C22 alloy cap + fittings (Buechi AG company) g of acetic acid and the autoclave are closed. The suspension is maintained at 50 ° C for 15 minutes. 317 g of 3-chloropropyl (methyldiethoxysilane) is metered into the suspension using a pump. The mixture was heated to 73 ° C with stirring and the temperature was maintained for 180 minutes. Then the mixture is cooled to 50 ° C and the autoclave is opened. GC analysis of the crude product gives the following composition in percent by area:

Ethanol 38.1 3-chloropropyl (methyldiethoxysilane) 0.9 3-mercaptopropyl (methyldiethoxysilane) 48,4

Based on the above values, the conversion is 98%.

The contents of the reactor are discharged, mixed with 400 g of pentane and filtered. The filter cake is washed with pentane. 1113 g of filtrate is obtained.

The isolated filtrate is neutralized with acetic acid. In a rotary evaporator under pressure from 20 to 600 mbar and at a temperature of from 60 to 80 ° C, the resulting solution of the product is freed from volatile components. The precipitated solid is separated by filtration. 251.4 g of a colorless liquid are obtained.

Example 18 (X is SH)

First, at room temperature, 100 g of NaSH (71% strength with 24 wt.% Water) with 400 g of ethanol (s) are loaded into an autoclave equipped with a glass double jacket and a Hastelloy C22 alloy cap + fittings (Buechi AG company) water content of 5 wt.%) and 18 g of acetic acid and the autoclave is closed. The suspension is maintained at 50 ° C for 15 minutes. 240 g of 3-chloropropyl (triethoxysilane) are metered into the suspension using a pump. The mixture is heated to 80 ° C with stirring and the temperature is maintained for 180 minutes. Then the mixture is cooled to 51 ° C and the autoclave is opened. The contents of the reactor are discharged and filtered. The filter cake is washed with ethanol (with a water content of 5 wt.%). 1049.9 g of filtrate is obtained. GC analysis of the filtrate indicates the following components in wt.% (Toluene is the internal standard):

Ethanol 55.1 3-chloropropyl (triethoxysilane) 2.1 3-mercaptopropyl (triethoxysilane) 16,4 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ 0.2 (EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ 2.1

If based on the above values (in wt.%), The conversion is 90%, and the selectivity of the reaction is 88%. The yield of crude product is 95%, based on the above values.

Example 19 (X is SH)

Initially, at room temperature, 100 g of NaSH (71% strength with 24 wt.% Water) with 400 g of ethanol (with water content of 5 wt.%), 46 g of NaHCO ₃ , 5.05 g of Na ₂ CO ₃ and 18 g of acetic acid and the autoclave was closed. The suspension is maintained at 51 ° C for 15 minutes. 240 g of 3-chloropropyl (triethoxysilane) are metered into the suspension using a pump. The mixture is heated to 81 ° C with stirring and the temperature is maintained for 90 minutes. Then the mixture is cooled to 51 ° C and the autoclave is opened. The contents of the reactor are discharged and filtered. The filter cake is washed with ethanol (with a water content of 5 wt.%). 1081.2 g of filtrate is obtained. GC analysis of the filtrate indicates the following components in wt.% (Toluene is the internal standard):

Ethanol 54 3-chloropropyl (triethoxysilane) 2.2 3-mercaptopropyl (triethoxysilane) 15.7 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ 0.2 (EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ 2.9

If based on the above values (in wt.%), The conversion is 89%, and the selectivity of the reaction is 83.5%. The yield of crude product is 95% based on the above values.

Example 20 (X is SH)

Initially, at room temperature, 100 g of NaSH (71% strength with 24 wt.% Water) with 400 g of ethanol (with water content of 5 wt.%), 46 g of NaHCO ₃ , 5.05 g of Na ₂ CO ₃ and 18 g of acetic acid and the autoclave was closed. The suspension is incubated for 15 min at 51 ° C. 240 g of 3-chloropropyl (triethoxysilane) are metered into the suspension using a pump. The mixture was heated to 81 ° C with stirring and the temperature was maintained for 120 minutes. Then the mixture is cooled to 44 ° C and the autoclave is opened. The contents of the reactor are discharged and filtered. The filter cake is washed with ethanol (with a water content of 5 wt.%). 1052.9 g of filtrate is obtained. GC analysis of the filtrate indicates the following components in wt.% (Toluene is the internal standard):

Ethanol 52,4 3-chloropropyl (triethoxysilane) one 3-mercaptopropyl (triethoxysilane) 16.8 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ 0.2 (EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ 0.9

If based on the above values (in wt.%), The conversion is 95%, and the selectivity of the reaction is 94%.

Example 21 (X is SH)

Initially, at room temperature, 100 g of NaSH (71% strength with 24 wt.% Water) with 400 g of ethanol are loaded into an autoclave equipped with a glass double jacket and a Hastelloy C22 alloy cap + fittings (manufactured by Buechi AG) g of Na ₂ HPO ₄ · 2H ₂ O, 17 g of KH ₂ PO ₄ and 18 g of acetic acid and the autoclave was closed. The suspension is maintained at elevated temperature for 15 minutes. 240 g of 3-chloropropyl (triethoxysilane) are metered into the suspension at a temperature ranging from 40 to 50 ° C. The mixture was heated to 89 ° C with stirring and the temperature was maintained for 90 minutes. Then the mixture is cooled to 50 ° C and the autoclave is opened. The contents of the reactor are discharged and filtered. The filter cake is washed with ethanol. 1109.2 g of filtrate is obtained. GC analysis of the filtered solution of the crude product gives in wt.% (Toluene is the internal standard):

Ethanol 57.4 3-chloropropyl (triethoxysilane) 2.2 3-mercaptopropyl (triethoxysilane) 14.3 (EtO) ₃ Si- (CH ₂ ) ₃ -S- (CH ₂ ) ₃ -Si (OEt) ₃ 0.3 (EtO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OEt) ₃ 2,8

In the crude reaction product,> 90 wt% of the silane used is contained in a non-hydrolyzed form.

If based on the values given in the table (wt.%), The conversion is 89%, and the selectivity of the reaction is 82%.

Claims (8)

1. The method of obtaining organosilanes of General formula I

wherein R are identical or different and denote C ₁ -C ₈ alkyl group, C ₁ -C ₈ alkenyl, C ₁ -C ₈ aryl or C ₁ -C ₈ aralkyl group or a OR 'group,
R 'are the same or different and denote a branched or straight chain monovalent C ₁ -C ₂₄ alkyl or α-alkenyl group, an aryl group, an aralkyl group, a hydrogen atom (-H), an aliphatic ether group O- (CR ^III ₂ ) -O- Alk or O- (CR ^III ₂ ) _at —O — Alk, or the aliphatic polyether group O- (CR ^III ₂ O) _at —Alk, or O- (CR ^III ₂ —CR ^III ₂ —O) _at —Alk, where y is from 2 to 20, R ^{III is} independently H or an alkyl group, and Alk is a branched or straight chain saturated or unsaturated aliphatic, aromatic and whether a mixed aliphatic / aromatic monovalent C ₁ -C ₃₀ hydrocarbon group,
R "denotes a branched or straight chain saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C ₁ -C ₃₀ hydrocarbon group which is optionally substituted with F, Cl, Br, I, HS, NH ₂ or NHR ',
X is S, if n is 2, am is a sulfur chain of average length from 1.5 to 4.5, and
X is SH, if n is 1 and m is 1, by the reaction of (halo-ganyl) alkoxysilane of formula II

in which R, R 'and R "have the above meanings, a Hal represents an atom of chlorine, bromine, fluorine or iodine,
with a sulfonating agent selected from the group consisting of alkali metal hydrosulfide, Me ₂ S metal sulfide, Me ₂ S _g metal polysulfide and any combination thereof, where Me is an alkali metal, NH ₄ or (alkaline earth metal) _1/2 , ag is from 1.5 to 8.0, and optionally additionally with sulfur and / or H ₂ S in alcohol, with the formation of a suspension of a crude product, characterized in that Me ₂ S or Me ₂ S _g contains more than 10 wt.% Water, and alkali metal hydrosulfide contains more than 3 wt.% water. 2. The method of producing organosilanes according to claim 1, characterized in that additives are added before, during or after the reaction. 3. The method of producing organosilanes according to claim 2, characterized in that the additives are non-alcoholic solvents, polar protic, aprotic, basic or acidic additives. 4. The method of producing organosilanes according to claims 1 to 3, characterized in that a solvent / water mixture is removed from the crude product suspension and the resulting organosilane of general formula I is separated from the solid material. 5. The method of producing organosilanes according to claims 1 to 3, characterized in that the solvent is removed from the suspension of the crude product, a mixture comprising organosilanes of the general formula (I) and solid material Me (Hal) are mixed with water containing at least one buffer , and the phases formed are separated. 6. The method of producing organosilanes according to claim 1, characterized in that in the case of organosilanes of the general formula I, where X is SH, m is 1 and n is 1, alkali metal hydrosulfide is used as the water-containing sulfonating reagent. 7. The method of producing organosilanes according to claim 1, characterized in that in the case of organosilanes of the general formula I, where X is S and m is from 3.5 to 4.5, Me ₂ S and sulfur are used as the water-containing sulfonating reagent. 8. The method of producing organosilanes according to claim 1, characterized in that in the case of organosilanes of the general formula I, where X is S and m is from 1.5 to 4.5, alkali metal hydrosulfides, Me ₂ , are used as aqueous sulfonating reagents. S, Me ₂ S _g and any necessary combinations thereof, and optionally additionally sulfur and / or H ₂ S, and the reaction is carried out in a closed vessel in the absence of air.