Indian Patents. 202676:PROCESS FOR THE PRODUCTION OF ORGANOSILYLALKYL POLYSULFANES

Title of Invention	PROCESS FOR THE PRODUCTION OF ORGANOSILYLALKYL POLYSULFANES
Abstract	The invention relates to a process for the production of organosilylalkyl polysulfanes by reacting an organosilylalkyl halide and an anhydrous or virtually anhydrous ionic sulfide and elementary sulfur, wherein the elementary sulfur and organosilylalkyl halide are suspended in a polar organic solvent and the ionic sulfide is added to this suspension.

Full Text	1 Process for the production of organosilylalkyl polysulfanes The present invention relates to a process for the production of organosilylalkyl polysulfanes. It is known that organosilylalkyl polysulfanes such as bis-(3-triethoxysilylpropyl)tetrasulfane (DE 2 141 159 and bis-(3-triethoxysilylpropyl)disulfane can be used as silane coupling agent or reinforcing additive in rubber mixtures filled with oxides. The rubber mixtures are used, inter alia, for industrial rubber articles and for parts of vehicle tyres, in particular for treads (DE 2 141 159, DE 2 212 239, US 3 978 103, US 4 048 206). Various processes for producing organosilylalkyl polysulfanes are described in the literature. In this respect processes that use industrially easily accessible organosilylalkyl halides represent the most economical and simplest alternative. These organosilylalkyl halides are reacted with ionic polysulfides, whereby the halide functions of two molecules are replaced by polysulfane units by nucleophilic substitution and thereby bonded to one another. In this process the preparation of the nucleophilic polysulfide presents the most difficulty. Of course, ionic polysulfides can be obtained relatively easily in aqueous phase according to a method known per se by reacting sulfur with alkali sulfide hydrates, alkali hydrogen sulfide hydrates or caustic soda and the resultant aqueous alkali polysulfide solutions can then be reacted with organosilylalkyl halides in a phase-transfer catalytic system to form the analogous polysulfanes (EP 694552, EP 794186, EP 839816). However, with the known process there is always the disadvantage that large proportions of the alkoxysilane starting material are converted into 2 ineffective solid polysiloxanes due to hydrolysis and condensation. The organosilane polysulfides produced according to the known process are also characterised by an unsatisfactory storage stability. These disadvantages can be avoided by working with anhydrous or virtually anhydrous starting substances in organic solution. US 5399739 and EP 705838 disclose processes in which ionic polysulfides are produced by reacting alcoholates with hydrogen sulfide, which in turn are then reacted with sulfur and the corresponding organosilylalkyl halide. The disadvantage of these processes is that hydrogen sulfide gas, which is problematic from the safety and toxicological aspects, and alcoholates, which are not very stable under storage, are used in the production of the anhydrous sulfide. A technically better solution for producing anhydrous or virtually anhydrous sulfides is to dry alkali sulfides, principally sodium sulfide hydrate, which are commercially available in large quantities. From JP 7228588 it is known that the drying process can be carried out azeotropically as well as in vacuo under heating, and the anhydrous or virtually anhydrous sulfides thus obtained can be reacted with sulfur to form alkali polysulfides.o These polysulfides in turn react with organosilylalkyl halides to form the corresponding polysulfanes. A similar process involving a variation of the azeotropic drying of the alkali sulfide is known from EP 795558. The disadvantage of these processes however is that a polysulfide first of all has to be produced in a preceding process step from the alkali sulfide and sulfur, and can only then be converted by reaction with the organosilylalkyl halide into the desired polysulfide. 3 In DE 19651849 a process is described in which the production of the polysulfide already takes place during the drying. The process step involving the polysulfide production can thus be avoided and cost savings can be made, which significantly improves the economy of the process. Further processes that likewise produce organosilylalkyl polysulfanes from anhydrous or virtually anhydrous ionic sulfides and.that avoid a preliminary polysulfide production stage are described in DE 19734295 and EP 949263. A common feature of all the cited processes is that an anhydrous polysulfide is mixed with a polar organic solvent and the organosilylalkyl halide is added to this solution/ suspension. However, highly coloured and often also unpleasantly smelling products are formed in such a procedure. The object of the invention is to provide a process in which organosilane polysulfides are produced that are only slightly coloured and have only a slight unpleasant odour. The present invention accordingly provides a process for the production of organosilylalkyl polysulfanes of the general formula R'R'R'siR'hS, (I) in which R1, R2, R3, which are identical to or different from one another, denote branched and unbranched alkyl and/or alkoxy 4 groups with a chain length of 1 - 8 C atoms, preferably 1 - 3 C atoms, aryl radicals, in particular phenyl, toluyl, benzyl, wherein at least one alkoxy group is present; R denotes a divalent alkylene radical with a chain length of 1 to 8 C atoms, preferably 1 to 5 C atoms, particularly preferably methylene, ethylene, i-propylene, n-propylene, i-but:ylene, n-butylene, n-pentylene, 2-methylbutylene, 3-methylbutylene, 1,3-dimethylpropylene and 2,3-dimethylpropylene, or - x is a number >1, preferably between 2 and 6, by reacting an organosilylalkyl halide of the general formula RaR2R3SiR4X (II) in which R1, R2, R3 and R* have the meanings given above, and X is chlorine, bromine or iodine, and an anhydrous or virtually anhydrous ionic sulfide of the general formula M+2S2" (III) in which M+ denotes an alkali metal cation, preferably a sodium or potassium cation, an ammonium ion, an alkaline earth metal cation or a zinc cation, and elementary sulfur, which is characterised in 5 that the elementary sulfur and organosilylalkyl halide are placed in a polar organic solvent and the anhydrous or virtually anhydrous ionic sulfide is added to this suspension. After the reaction the organosilylalkyl polysulfane can be isolated by filtering off the precipitated halide and separating the solvent by distillation. On account of the susceptibility of the organosilylalkyl halide (II) to undergo hydrolysis, the ionic sulfides (III) must be anhydrous or virtually anhydrous. Virtually anhydrous ionic sulfides (III) are understood to be compounds according to formula (III) containing at most 10 wt.%, preferably 0 - 5 wt.%, and particularly preferably 0 - 2 wt.% of water. The virtually anhydrous ionic sulfides (III) can be obtained in various ways: Reaction of alkali metal alcoholates with hydrogen sulfide (EP 0 705 838). Reaction of ammonia gas with hydrogen sulfide (DE 26 48 241) . Drying alkali sulfide hydrates (DE 196 10 281, JP 7 228 588 and DE 196 51 849). In this connection it is unimportant whether the drying of the alkali sulfide hydrates is carried out azeotropically or by heating in vacuo. Preferably, the required ionic sulfide may be prepared according to the process described in DE 196 51 849. The ionic sulfide (III) may, without influencing the reaction yield, be used as a ground powder as well as in the form of small platelets, such as are present in the case of the commercially available alkali sulfide hydrates. 6 The amount of ionic sulfide (III) necessary for the reaction may be added in one lot or in partial amounts to the suspension consisting of the solvent, organosilylalkyl halide (II) and elementary sulfur. The ionic sulfide (III) may be added continuously or discontinuously. The sulfur may be added in solid form, for example as a commercially available sulfur powder, or granules, or in molten form. In order to accelerate the course of the reaction the sulfur may be used in finely divided form, for example as finely ground sulfur powder or as fine droplets of atomised melt. As organic solvent there may in principle be used all polar solvents in which the ionic sulfide (III)'is at least partially soluble, and which do not react with the organosilylalkyl halide (II). Linear or branched alcohols with 1 - 8 C atoms, such as for example methyl, ethyl, propyl, butyl or pentyl alcohol, cycloalkyl alcohols with 5 - 8 C atoms, phenol or benzyl alcohol, may preferably be used as organic solvent. In order to avoid a transesterification, it may be more expedient to use the alcohol corresponding in each case to the groups R1, R2 and R3. Optionally, it may also be advantageous to use a mixture of these alcohols, for example if different alkoxy groups R1, R2, R3 are present in the compound II. The molar ratios of the individual reactants to one another are governed by the mean sulfur chain length that is to be established in the organosilylalkyl polysulfane (I) to be produced therewith, and by the residual content of organosilylalkyl halides (II) that is to be present in the end 7 product. Accordingly the molar ratio of the ionic sulfide of the formula (III) to the elementary sulfur that is used controls the mean polysulfane chain length in the end product. For the process according to the invention ionic sulfide:sulfur may be used in a molar ratio of at least 1:0.1, preferably 1:0.8 to 1:5.2. The molar ratio of ionic sulfide to the organosilylalkyl halide determines the residual content of the starting material in the end product. For the process according to the invention a ratio of ionic sulfide to organosilylalkyl halide of 1 : 1 to 1 : 3 may be chosen, preferably a ratio of 1 : 1.5 to 1 : 2.2. The reaction may be carried out with the exclusion of air and water (moisture) in order to suppress or largely avoid the formation of secondary products. The reaction may be carried out at elevated temperature- In this connection it is immaterial for the process according to the invention whether, in order to reach the reaction temperature, the reaction mixture is heated externally or is heated solely by the heat released due to the exothermic reaction. The reaction may be carried out between room temperature and 200°C, preferably between 40°C and the boiling point of the solvent that is used. The reaction may be carried out under reduced pressure, normal pressure or slight superatmospheric pressure. The organosilane polysulfides produced by the process according to the invention have the advantage that they are less coloured and have a less unpleasant odour than the known organosilane polysulfides. 8 Examples: Comparison example 1: Preparation of bis(triethoxysilyl-propyl)disulfane 17.8 kg of virtually anhydrous sodium sulfide are mixed with 190 1 of ethanol and added to an enamelled 500 1 capacity reactor. This is followed by the addition through a fine nozzle of 13.85 kg of sulfur in molten form. The mixture is heated to 50°C and 190 1 of 3-chloropropyltri-ethoxysilane are metered in within 10 minutes. On account of the exothermic reaction the temperature of the reactor contents rises to 74°C. A further 4.45 kg of virtually anhydrous sodium sulfide are added at this temperature. Three further portions of sodium sulfide are added at intervals of in each case 5 minutes, the temperature of the reactor contents rising to 82°C. After completion of the sodium sulfide addition the reaction mixture is kept for 1.5 hours at 82 - 83°C and the sodium chloride that has precipitated is separated after cooling the mixture. A yellow product is obtained after evaporating the reaction mixture in vacuo and renewed fine filtration. HPLC analysis confirms the presence of a product with a mean polysulfane chain length of 2. Example 1: Preparation of bis(triethoxysilylpropyl)-disulfane 13.85 kg of sulfur in molten form is metered in through a fine nozzle into a mixture of 190 1 of ethanol and 190 1 of 3-chloropropyltriethoxysilane contained in the reactor of comparison example 1. 17.8 kg of virtually anhydrous sodium sulfide are then added, the temperature of the reactor contents rising to 60°C due to the heat released in the exothermic reaction. Four further portions of in each case 4.45 kg of sodium sulfide are added starting at this 9 temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises further to 82°C. After completion of the sodium sulfide addition the reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms the presence of a polysulfane mixture with a mean' chain length of 2. Example 2: Preparation of bis(triethoxysilylpropyl)-disulfane 129 1 of ethanol are placed in the reactor of comparison example 1, followed by the addition of 129 1 of 3-chloro-propyltriethoxysilane. 13.85 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture. 17.8 kg of virtually anhydrous sodium sulfide are next added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents thereby rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 3: Preparation of bis{triethoxysilylpropyl)-disulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 13.85 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture. 10 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 4: Preparation of bis(triethoxysilylpropyl)-disulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 13.85 kg of sulfur in molten form are added through a fine nozzle. 129 1 of 3- chloropropyltriethoxysilane are added to the mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. 11 Example 5: Preparation of bis(triethoxysilylpropyl)-disulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 13.85 kg of sulfur in molten form are metered in through a fine nozzle. 129 1 of ethanol are added to the mixture, followed by 17.8 kg of virtually anhydrous sodium sulfide. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 6: Preparation of bis(triethoxysilylpropyl)-disulfane A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyltriethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of granules are metered in, followed by the addition of 17.8 kg of virtually anhydrous sodium sulfide. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC 12 analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 7: Preparation of bis(triethoxysilylpropyl)-disulfane 129 1 of ethanol are placed in the reactor of comparison example 1, followed by the addition of 129 1 of 3-chloropropyltriethoxysilane. 13.85 kg of sulfur in the form of granules are metered in to the resultant mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The' temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45'kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes.' The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 8: Preparation of bis(triethoxysilylpropyl)-disulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1, followed by the addition of 129 1 of ethanol. 13.85 kg of sulfur in the form of granules are metered in to the resultant mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The 13 temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 9: Preparation of bis(triethoxysilylpropyl)-disulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of granules are then metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 10: Preparation of bis{triethoxysilylpropyl}-disulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of granules are metered in. 129 1 of ethanol are added to the mixture, followed by the addition of 17.8 kg of virtually anhydrous sodium sulfide. The temperature of 14 the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 11: Preparation of bis{triethoxysilylpropyl)-disulfane A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of a powder are metered in. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 12: Preparation of bis(triethoxysilylpropyl)-disulfane 15 129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added. 13.85 kg of sulfur in the form of a powder are metered in to the resultant mixture. 17.8 kg of virtually-anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 13: Preparation of bis(triethoxysilylpropyl)-disulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added. 13.85 kg of sulfur in the form of a powder are metered in to the resultant mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. 16 Example 14: Preparation of bis {triethoxysilylpropyl) -disulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of a powder are metered in. 129 1 of 3-chloropropyltriethoxysxlane are added to the mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 15: Preparation of bis(triethoxysilylpropyl)-disulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of a powder are metered in. 129 1 of ethanol are added to the mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 17 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2. Example 16: Preparation of bis(triethoxysilylpropyl)-disulfane A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in molten form are then metered in through a fine nozzle. 35.6 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 82°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2, though the mixture has a high monosulfane content. Example 17: Preparation of bis(triethoxysilylpropyl)-disulfane A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of granules are metered in. 35.6 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 82°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the 18 presence of a polysulfane mixture with a mean chain length of 2, though the mixture has a high monosulfane content. Example 18: Preparation of bis(triethoxysilylpropyl)-disulfane A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of a powder are metered in. 35.6 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 82°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2, though the mixture has a high monosulfane content. Comparison Example 2: Preparation of bis{triethoxysilylpropyl) tetrasulfane 23 kg of virtually dry sodium sulfide in 125 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are added through a fine nozzle. The mixture is heated to 55°C and 129 1 of 3-chloropropyl-triethoxysilane are metered in at this temperature within 50 minutes. The temperature of the reactor contents rises to 77°C on account of the heat released in the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. Precipitated sodium chloride is separated. An orange product is obtained after evaporating the reaction mixture in vacuo and renewed fine filtration. HPLC analysis confirms the presence of a product with a mean polysulfane chain length of 4. 19 Example 19: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 28.4 kg of sulfur in molten form is metered through a fine nozzle into a mixture of 129 1 of ethanol and 129 1 of 3-chloropropyltriethoxysilane contained in the reactor of comparison example 1. 23.0 kg of virtually anhydrous sodium sulfide are then added, the temperature of the reactor contents rising to 83°C on account of the heat released in the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms the presence of a polysulfane mixture with a mean chain length of 4. Example 20: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C due to the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 20 Example 21: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 22: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are metered in through a fine nozzle. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 21 Example 23: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are metered in through a fine nozzle. 129 1 of ethanol are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 24: Preparation of bis{triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in the form of granules are metered in to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 22 Example 25: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in the form of granules are metered in to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 26: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of granules are metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 23 Example 27: Preparation of bis{triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of granules are metered in. 129 1 of ethanol are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 28: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in the form of a powder are metered in to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 24 Example 29: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in the form of a powder are metered in to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 30: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of a powder are metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 25 Example 31: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of a powder are added thereto. 129 1 of ethanol are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 32: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 28.4 kg of sulfur in molten form is metered through a fine nozzle into a mixture of 129 1 of ethanol and 129 1 of 3-chloropropyltriethoxysilane in the reactor of comparison example 1. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 26 Example 33: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in molten form are metered through a fine nozzle in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 34: Preparation of bis{triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 27 Example 35: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are added thereto through a fine nozzle. 129 1 of 3-chloropropyl-triethoxysilane are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 36: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are metered in through a fine nozzle. 129 1 of ethanol are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 28 Example 37: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 28.4 kg of sulfur in the form of granules are metered in to a mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane in the reactor of comparison example 1. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 38: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in the form of granules are metered in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 29 Example 39: Preparation of bis (triethoxysilylpropyl) -tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in the form of granules are metered in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 40: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of granules are metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 30 Example 41: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of granules are metered in. 129 1 of ethanol are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept'for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 42: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 28.4 kg of sulfur in the form of a powder are metered in to a mixture of 129 1 of ethanol and 129 1 of 3-chloropropyltriethoxysilane in the reactor of comparison example 1. A total of 23.0 kg of virtually anhydrous sodium sulfide is then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 31 Example 43: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in the form of a powder are metered in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 44: Preparation of bis(triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in the form of a powder are metered in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 32 Example 45: Preparation of bis{triethoxysilylpropyl)-tetrasulfane 129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of a powder are metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. Example 46: Preparation of bis{triethoxysilylpropyl)-tetrasulfane 129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of a powder are metered in. 129 1 of ethanol are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4. 33 WE CLAIM 1. Process for the production of organosilylalkyl polysulfanes of the general formula (R1RaR3SiR4)2Sx (I) in which R1, R2, R3, which are identical to or different from one another, denote branched and unbranched alkyl and/or alkoxy groups with a chain length of 1 - 8 C atoms, aryl radicals, wherein at least one alkoxy group is present, R4 denotes a divalent alkylene radical with a chain length of 1 - 8 C atoms, or -(CH2)n-C6H"~(CH2)n- where n = 1 - 4; r x is a number >ljby reaction of an organosilylalkyl halide of the general formula R'R'R'SIR'X (II) in which R1, R2, R3 and R* have the meanings given above, and X is chlorine, bromine or iodine, and an anhydrous or virtually anhydrous ionic sulfide of the general formula M\S2~ (III 34 in which M* denotes an alkali metal cation, an ammonium ion, an alkaline earth metal cation or a zinc cation, and elementary sulfur, characterised in that the elementary sulfur and organosilylalkyl halide are placed in a polar organic solvent and the anhydrous or virtually anhydrous ionic sulfide is added to this suspension. 2. Process for the production of organosilylalkyl polysulfanes according to claim 1, characterised in that an ionic sulfide containing at most 10 wt.% of water is used. 3 . Process for the production of organosilylalkyl polysulfanes according to claim 1, characterised in that linear or branched alcohols with 1 - 8 C atoms are used as organic solvent. The invention relates to a process for the production of organosilylalkyl polysulfanes by reacting an organosilylalkyl halide and an anhydrous or virtually anhydrous ionic sulfide and elementary sulfur, wherein the elementary sulfur and organosilylalkyl halide are suspended in a polar organic solvent and the ionic sulfide is added to this suspension.

Full Text

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Process for the production of organosilylalkyl polysulfanes
The present invention relates to a process for the production of organosilylalkyl polysulfanes.
It is known that organosilylalkyl polysulfanes such as bis-(3-triethoxysilylpropyl)tetrasulfane (DE 2 141 159 and bis-(3-triethoxysilylpropyl)disulfane can be used as silane coupling agent or reinforcing additive in rubber mixtures filled with oxides. The rubber mixtures are used, inter alia, for industrial rubber articles and for parts of vehicle tyres, in particular for treads (DE 2 141 159, DE 2 212 239, US 3 978 103, US 4 048 206).
Various processes for producing organosilylalkyl polysulfanes are described in the literature. In this respect processes that use industrially easily accessible organosilylalkyl halides represent the most economical and simplest alternative. These organosilylalkyl halides are reacted with ionic polysulfides, whereby the halide functions of two molecules are replaced by polysulfane units by nucleophilic substitution and thereby bonded to one another.
In this process the preparation of the nucleophilic polysulfide presents the most difficulty. Of course, ionic polysulfides can be obtained relatively easily in aqueous phase according to a method known per se by reacting sulfur with alkali sulfide hydrates, alkali hydrogen sulfide hydrates or caustic soda and the resultant aqueous alkali polysulfide solutions can then be reacted with organosilylalkyl halides in a phase-transfer catalytic system to form the analogous polysulfanes (EP 694552, EP 794186, EP 839816). However, with the known process there is always the disadvantage that large proportions of the alkoxysilane starting material are converted into

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ineffective solid polysiloxanes due to hydrolysis and condensation. The organosilane polysulfides produced according to the known process are also characterised by an unsatisfactory storage stability.
These disadvantages can be avoided by working with anhydrous or virtually anhydrous starting substances in organic solution. US 5399739 and EP 705838 disclose processes in which ionic polysulfides are produced by reacting alcoholates with hydrogen sulfide, which in turn are then reacted with sulfur and the corresponding organosilylalkyl halide. The disadvantage of these processes is that hydrogen sulfide gas, which is problematic from the safety and toxicological aspects, and alcoholates, which are not very stable under storage, are used in the production of the anhydrous sulfide.
A technically better solution for producing anhydrous or virtually anhydrous sulfides is to dry alkali sulfides, principally sodium sulfide hydrate, which are commercially available in large quantities. From JP 7228588 it is known that the drying process can be carried out azeotropically as well as in vacuo under heating, and the anhydrous or virtually anhydrous sulfides thus obtained can be reacted with sulfur to form alkali polysulfides.o These polysulfides in turn react with organosilylalkyl halides to form the corresponding polysulfanes.
A similar process involving a variation of the azeotropic drying of the alkali sulfide is known from EP 795558.
The disadvantage of these processes however is that a polysulfide first of all has to be produced in a preceding process step from the alkali sulfide and sulfur, and can only then be converted by reaction with the organosilylalkyl halide into the desired polysulfide.

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In DE 19651849 a process is described in which the production of the polysulfide already takes place during the drying. The process step involving the polysulfide production can thus be avoided and cost savings can be made, which significantly improves the economy of the process.
Further processes that likewise produce organosilylalkyl polysulfanes from anhydrous or virtually anhydrous ionic sulfides and.that avoid a preliminary polysulfide production stage are described in DE 19734295 and EP 949263.
A common feature of all the cited processes is that an anhydrous polysulfide is mixed with a polar organic solvent and the organosilylalkyl halide is added to this solution/ suspension. However, highly coloured and often also unpleasantly smelling products are formed in such a procedure.
The object of the invention is to provide a process in which organosilane polysulfides are produced that are only slightly coloured and have only a slight unpleasant odour.
The present invention accordingly provides a process for the production of organosilylalkyl polysulfanes of the general formula
R'R'R'siR'hS, (I)
in which
R1, R2, R3, which are identical to or different from one another, denote branched and unbranched alkyl and/or alkoxy

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groups with a chain length of 1 - 8 C atoms, preferably
1 - 3 C atoms, aryl radicals, in particular phenyl, toluyl,
benzyl, wherein at least one alkoxy group is present;
R denotes a divalent alkylene radical with a chain
length of 1 to 8 C atoms, preferably 1 to 5 C atoms, particularly preferably methylene, ethylene, i-propylene, n-propylene, i-but:ylene, n-butylene, n-pentylene, 2-methylbutylene, 3-methylbutylene, 1,3-dimethylpropylene and 2,3-dimethylpropylene, or - x is a number >1, preferably between 2 and 6,
by reacting an organosilylalkyl halide of the general formula
RaR2R3SiR4X (II)
in which
R1, R2, R3 and R* have the meanings given above, and
X is chlorine, bromine or iodine,
and an anhydrous or virtually anhydrous ionic sulfide of the general formula
M+2S2" (III)
in which M+ denotes an alkali metal cation, preferably a sodium or potassium cation, an ammonium ion, an alkaline earth metal cation or a zinc cation,
and elementary sulfur, which is characterised in

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that the elementary sulfur and organosilylalkyl halide are placed in a polar organic solvent and the anhydrous or virtually anhydrous ionic sulfide is added to this suspension.
After the reaction the organosilylalkyl polysulfane can be isolated by filtering off the precipitated halide and separating the solvent by distillation.
On account of the susceptibility of the organosilylalkyl halide (II) to undergo hydrolysis, the ionic sulfides (III) must be anhydrous or virtually anhydrous. Virtually anhydrous ionic sulfides (III) are understood to be compounds according to formula (III) containing at most 10 wt.%, preferably 0 - 5 wt.%, and particularly preferably 0 - 2 wt.% of water. The virtually anhydrous ionic sulfides (III) can be obtained in various ways:
Reaction of alkali metal alcoholates with hydrogen sulfide (EP 0 705 838).
Reaction of ammonia gas with hydrogen sulfide (DE 26 48 241) .
Drying alkali sulfide hydrates (DE 196 10 281, JP 7 228 588 and DE 196 51 849).
In this connection it is unimportant whether the drying of the alkali sulfide hydrates is carried out azeotropically or by heating in vacuo. Preferably, the required ionic sulfide may be prepared according to the process described in DE 196 51 849. The ionic sulfide (III) may, without influencing the reaction yield, be used as a ground powder as well as in the form of small platelets, such as are present in the case of the commercially available alkali sulfide hydrates.

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The amount of ionic sulfide (III) necessary for the reaction may be added in one lot or in partial amounts to the suspension consisting of the solvent, organosilylalkyl halide (II) and elementary sulfur. The ionic sulfide (III) may be added continuously or discontinuously.
The sulfur may be added in solid form, for example as a commercially available sulfur powder, or granules, or in molten form.
In order to accelerate the course of the reaction the sulfur may be used in finely divided form, for example as finely ground sulfur powder or as fine droplets of atomised melt.
As organic solvent there may in principle be used all polar solvents in which the ionic sulfide (III)'is at least partially soluble, and which do not react with the organosilylalkyl halide (II).
Linear or branched alcohols with 1 - 8 C atoms, such as for example methyl, ethyl, propyl, butyl or pentyl alcohol, cycloalkyl alcohols with 5 - 8 C atoms, phenol or benzyl alcohol, may preferably be used as organic solvent.
In order to avoid a transesterification, it may be more expedient to use the alcohol corresponding in each case to the groups R1, R2 and R3. Optionally, it may also be advantageous to use a mixture of these alcohols, for example if different alkoxy groups R1, R2, R3 are present in the compound II.
The molar ratios of the individual reactants to one another are governed by the mean sulfur chain length that is to be established in the organosilylalkyl polysulfane (I) to be produced therewith, and by the residual content of organosilylalkyl halides (II) that is to be present in the end

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product. Accordingly the molar ratio of the ionic sulfide of the formula (III) to the elementary sulfur that is used controls the mean polysulfane chain length in the end product. For the process according to the invention ionic sulfide:sulfur may be used in a molar ratio of at least 1:0.1, preferably 1:0.8 to 1:5.2.
The molar ratio of ionic sulfide to the organosilylalkyl halide determines the residual content of the starting material in the end product. For the process according to the invention a ratio of ionic sulfide to organosilylalkyl halide of 1 : 1 to 1 : 3 may be chosen, preferably a ratio of 1 : 1.5 to 1 : 2.2.
The reaction may be carried out with the exclusion of air and water (moisture) in order to suppress or largely avoid the formation of secondary products. The reaction may be carried out at elevated temperature- In this connection it is immaterial for the process according to the invention whether, in order to reach the reaction temperature, the reaction mixture is heated externally or is heated solely by the heat released due to the exothermic reaction. The reaction may be carried out between room temperature and 200°C, preferably between 40°C and the boiling point of the solvent that is used. The reaction may be carried out under reduced pressure, normal pressure or slight superatmospheric pressure.
The organosilane polysulfides produced by the process according to the invention have the advantage that they are less coloured and have a less unpleasant odour than the known organosilane polysulfides.

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Examples:
Comparison example 1: Preparation of bis(triethoxysilyl-propyl)disulfane
17.8 kg of virtually anhydrous sodium sulfide are mixed with 190 1 of ethanol and added to an enamelled 500 1 capacity reactor. This is followed by the addition through a fine nozzle of 13.85 kg of sulfur in molten form. The mixture is heated to 50°C and 190 1 of 3-chloropropyltri-ethoxysilane are metered in within 10 minutes. On account of the exothermic reaction the temperature of the reactor contents rises to 74°C. A further 4.45 kg of virtually anhydrous sodium sulfide are added at this temperature. Three further portions of sodium sulfide are added at intervals of in each case 5 minutes, the temperature of the reactor contents rising to 82°C. After completion of the sodium sulfide addition the reaction mixture is kept for 1.5 hours at 82 - 83°C and the sodium chloride that has precipitated is separated after cooling the mixture. A yellow product is obtained after evaporating the reaction mixture in vacuo and renewed fine filtration. HPLC analysis confirms the presence of a product with a mean polysulfane chain length of 2.
Example 1: Preparation of bis(triethoxysilylpropyl)-disulfane
13.85 kg of sulfur in molten form is metered in through a fine nozzle into a mixture of 190 1 of ethanol and 190 1 of 3-chloropropyltriethoxysilane contained in the reactor of comparison example 1. 17.8 kg of virtually anhydrous sodium sulfide are then added, the temperature of the reactor contents rising to 60°C due to the heat released in the exothermic reaction. Four further portions of in each case 4.45 kg of sodium sulfide are added starting at this

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temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises further to 82°C. After completion of the sodium sulfide addition the reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms the presence of a polysulfane mixture with a mean' chain length of 2.
Example 2: Preparation of bis(triethoxysilylpropyl)-disulfane
129 1 of ethanol are placed in the reactor of comparison example 1, followed by the addition of 129 1 of 3-chloro-propyltriethoxysilane. 13.85 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture. 17.8 kg of virtually anhydrous sodium sulfide are next added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents thereby rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 3: Preparation of bis{triethoxysilylpropyl)-disulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 13.85 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture.

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17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 4: Preparation of bis(triethoxysilylpropyl)-disulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 13.85 kg of sulfur in molten form are added through a fine nozzle. 129 1 of 3-
chloropropyltriethoxysilane are added to the mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.

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Example 5: Preparation of bis(triethoxysilylpropyl)-disulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 13.85 kg of sulfur in molten form are metered in through a fine nozzle. 129 1 of ethanol are added to the mixture, followed by 17.8 kg of virtually anhydrous sodium sulfide. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 6: Preparation of bis(triethoxysilylpropyl)-disulfane
A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyltriethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of granules are metered in, followed by the addition of 17.8 kg of virtually anhydrous sodium sulfide. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC

12
analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 7: Preparation of bis(triethoxysilylpropyl)-disulfane
129 1 of ethanol are placed in the reactor of comparison example 1, followed by the addition of 129 1 of 3-chloropropyltriethoxysilane. 13.85 kg of sulfur in the form of granules are metered in to the resultant mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The' temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45'kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes.' The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 8: Preparation of bis(triethoxysilylpropyl)-disulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1, followed by the addition of 129 1 of ethanol. 13.85 kg of sulfur in the form of granules are metered in to the resultant mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The

13
temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 9: Preparation of bis(triethoxysilylpropyl)-disulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of granules are then metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 10: Preparation of bis{triethoxysilylpropyl}-disulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of granules are metered in. 129 1 of ethanol are added to the mixture, followed by the addition of 17.8 kg of virtually anhydrous sodium sulfide. The temperature of

14
the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 11: Preparation of bis{triethoxysilylpropyl)-disulfane
A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of a powder are metered in. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 12: Preparation of bis(triethoxysilylpropyl)-disulfane

15
129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added. 13.85 kg of sulfur in the form of a powder are metered in to the resultant mixture. 17.8 kg of virtually-anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 13: Preparation of bis(triethoxysilylpropyl)-disulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added. 13.85 kg of sulfur in the form of a powder are metered in to the resultant mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.

16
Example 14: Preparation of bis {triethoxysilylpropyl) -disulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of a powder are metered in. 129 1 of 3-chloropropyltriethoxysxlane are added to the mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 15: Preparation of bis(triethoxysilylpropyl)-disulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of a powder are metered in. 129 1 of ethanol are added to the mixture. 17.8 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 60°C on account of the exothermic reaction. 4 further portions of in each case 4.45 kg of sodium sulfide are added starting at this temperature at intervals of in each case 5 minutes. The temperature of the reactor contents rises to 82°C. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example

17
1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2.
Example 16: Preparation of bis(triethoxysilylpropyl)-disulfane
A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in molten form are then metered in through a fine nozzle. 35.6 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 82°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2, though the mixture has a high monosulfane content.
Example 17: Preparation of bis(triethoxysilylpropyl)-disulfane
A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of granules are metered in. 35.6 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 82°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the

18
presence of a polysulfane mixture with a mean chain length of 2, though the mixture has a high monosulfane content.
Example 18: Preparation of bis(triethoxysilylpropyl)-disulfane
A mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane is placed in the reactor of comparison example 1. 13.85 kg of sulfur in the form of a powder are metered in. 35.6 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 82°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. An almost water-white product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 2, though the mixture has a high monosulfane content.
Comparison Example 2: Preparation of bis{triethoxysilylpropyl) tetrasulfane
23 kg of virtually dry sodium sulfide in 125 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are added through a fine nozzle. The mixture is heated to 55°C and 129 1 of 3-chloropropyl-triethoxysilane are metered in at this temperature within 50 minutes. The temperature of the reactor contents rises to 77°C on account of the heat released in the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. Precipitated sodium chloride is separated. An orange product is obtained after evaporating the reaction mixture in vacuo and renewed fine filtration. HPLC analysis confirms the presence of a product with a mean polysulfane chain length of 4.

19
Example 19: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
28.4 kg of sulfur in molten form is metered through a fine nozzle into a mixture of 129 1 of ethanol and 129 1 of 3-chloropropyltriethoxysilane contained in the reactor of comparison example 1. 23.0 kg of virtually anhydrous sodium sulfide are then added, the temperature of the reactor contents rising to 83°C on account of the heat released in the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms the presence of a polysulfane mixture with a mean chain length of 4.
Example 20: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C due to the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

20
Example 21: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 22: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are metered in through a fine nozzle. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

21
Example 23: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are metered in through a fine nozzle. 129 1 of ethanol are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 24: Preparation of bis{triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in the form of granules are metered in to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

22
Example 25: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in the form of granules are metered in to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 26: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of granules are metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

23
Example 27: Preparation of bis{triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of granules are metered in. 129 1 of ethanol are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 28: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in the form of a powder are metered in to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

24
Example 29: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in the form of a powder are metered in to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 30: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of a powder are metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

25
Example 31: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of a powder are added thereto. 129 1 of ethanol are added to the resultant mixture. 23.0 kg of virtually anhydrous sodium sulfide are then added. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 32: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
28.4 kg of sulfur in molten form is metered through a fine nozzle into a mixture of 129 1 of ethanol and 129 1 of 3-chloropropyltriethoxysilane in the reactor of comparison example 1. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

26
Example 33: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in molten form are metered through a fine nozzle in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 34: Preparation of bis{triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in molten form are metered through a fine nozzle into the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

27
Example 35: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are added thereto through a fine nozzle. 129 1 of 3-chloropropyl-triethoxysilane are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 36: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in molten form are metered in through a fine nozzle. 129 1 of ethanol are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

28
Example 37: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
28.4 kg of sulfur in the form of granules are metered in to a mixture of 129 1 of ethanol and 129 1 of 3-chloropropyl-triethoxysilane in the reactor of comparison example 1. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 38: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in the form of granules are metered in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

29
Example 39: Preparation of bis (triethoxysilylpropyl) -tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in the form of granules are metered in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 40: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of granules are metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

30
Example 41: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of granules are metered in. 129 1 of ethanol are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept'for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 42: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
28.4 kg of sulfur in the form of a powder are metered in to a mixture of 129 1 of ethanol and 129 1 of 3-chloropropyltriethoxysilane in the reactor of comparison example 1. A total of 23.0 kg of virtually anhydrous sodium sulfide is then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 -83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

31
Example 43: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 129 1 of 3-chloropropyltriethoxysilane are added thereto. 28.4 kg of sulfur in the form of a powder are metered in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 44: Preparation of bis(triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 129 1 of ethanol are added thereto. 28.4 kg of sulfur in the form of a powder are metered in to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

32
Example 45: Preparation of bis{triethoxysilylpropyl)-tetrasulfane
129 1 of ethanol are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of a powder are metered in. 129 1 of 3-chloropropyltriethoxysilane are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.
Example 46: Preparation of bis{triethoxysilylpropyl)-tetrasulfane
129 1 of 3-chloropropyltriethoxysilane are placed in the reactor of comparison example 1. 28.4 kg of sulfur in the form of a powder are metered in. 129 1 of ethanol are added to the resultant mixture. A total of 23.0 kg of virtually anhydrous sodium sulfide are then added in 10 equal portions at intervals of in each case 7 minutes. The temperature of the reactor contents rises to 83°C on account of the exothermic reaction. The reaction mixture is kept for a further 1.5 hours at 82 - 83°C and then cooled. The reaction mixture is worked up as in comparison example 1. A yellow product is obtained. HPLC analysis confirms in this case too the presence of a polysulfane mixture with a mean chain length of 4.

33
WE CLAIM
1. Process for the production of organosilylalkyl polysulfanes of the general formula
(R1RaR3SiR4)2Sx (I)
in which
R1, R2, R3, which are identical to or different from one another, denote branched and unbranched alkyl and/or alkoxy groups with a chain length of 1 - 8 C atoms, aryl radicals, wherein at least one alkoxy group is present,
R4 denotes a divalent alkylene radical with a chain length of 1 - 8 C atoms, or -(CH2)n-C6H"~(CH2)n- where n = 1 - 4;
r
x is a number >ljby
reaction of an organosilylalkyl halide of the general formula
R'R'R'SIR'X (II)
in which
R1, R2, R3 and R* have the meanings given above, and
X is chlorine, bromine or iodine,
and an anhydrous or virtually anhydrous ionic sulfide of the general formula
M\S2~ (III

34
in which M* denotes an alkali metal cation, an ammonium ion, an alkaline earth metal cation or a zinc cation,
and elementary sulfur, characterised in that the elementary sulfur and organosilylalkyl halide are placed in a polar organic solvent and the anhydrous or virtually anhydrous ionic sulfide is added to this suspension.
2. Process for the production of organosilylalkyl
polysulfanes according to claim 1, characterised in that an ionic sulfide containing at most 10 wt.% of water is used.
3 . Process for the production of organosilylalkyl
polysulfanes according to claim 1, characterised in that linear or branched alcohols with 1 - 8 C atoms are used as organic solvent.
The invention relates to a process for the production of organosilylalkyl polysulfanes by reacting an organosilylalkyl halide and an anhydrous or virtually anhydrous ionic sulfide and elementary sulfur, wherein the elementary sulfur and organosilylalkyl halide are suspended in a polar organic solvent and the ionic sulfide is added to this suspension.

Documents:

00117-cal-2001 abstract.pdf

00117-cal-2001 claims.pdf

00117-cal-2001 correspondence.pdf

00117-cal-2001 description(complete).pdf

00117-cal-2001 form-1.pdf

00117-cal-2001 form-18.pdf

00117-cal-2001 form-2.pdf

00117-cal-2001 form-3.pdf

00117-cal-2001 form-5.pdf

00117-cal-2001 form-6.pdf

00117-cal-2001 g.p.a.pdf

00117-cal-2001 letters patent.pdf

00117-cal-2001 priority document others.pdf

00117-cal-2001 priority document.pdf

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Patent Number

202676

Indian Patent Application Number

117/CAL/2001

PG Journal Number

09/2007

Publication Date

02-Mar-2007

Grant Date

02-Mar-2007

Date of Filing

26-Feb-2001

Name of Patentee

DEGUSSA AG

Applicant Address

BENNIGSENPLATZ 1 D-40474 DUSSELDORF

Inventors:

#	Inventor's Name	Inventor's Address
1	MICHEL RUDOLF	JOSEFSTRASSE 36, D-63579 FREIGERICHT
2	DR.JORG MUNZENBERG	forsthausstrasse 11, D-63457 HANAU
3	WERNER WILL	SCHULSTRASSE 46, D-63571 GELNHAUSEN
4	GERD RAINHARD ZEZULKA	AN DER MAINBRUCKE 19, D-63456 HANAU

PCT International Classification Number

C 07 F 007/08

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	10009790.1	2000-03-01	Germany