Method for preparing polysulfur silane

Abstract

By making the silane of formula II in the specification and one or more metal sulfides of formula III in the specification in an aqueous R 1 A method for preparing a polysulfur silane of formula I in the specification by reacting in an aqueous R 1 The process stream from the reaction in the OH solution is combined with the washing solution from step d, and b. the solvent R is removed by distillation 1 ‑OH and water, c. subjecting the remaining suspension comprising the polysulfur silane of formula I and the process salt to filtration or sedimentation, and d. treating the process salt of step c with a solvent R 1 ‑OH and then dried, the solvent R 1 The washing solution of -OH, water and the polysulfur silane of formula I is recycled to process step a.

Description

Technical Field

[0001] The present invention provides a method for preparing polysulfane silane. Background Art

[0002] EP 1130023 discloses a compound of formula R 1 R 2 R 3 Si-R 4 -X organosilylalkyl halide preparation formula (R 1 R 2 R 3 Si-R 4 -) 2 S q The reaction is carried out by adding a suspension of anhydrous or nearly anhydrous ionic sulfide to elemental sulfur and an organic silylalkyl halide in a polar organic solvent. Since the Si-alkoxy bond of the organic silylalkyl halide is easily hydrolyzed, the ionic sulfide must be anhydrous or nearly anhydrous.

[0003] EP 1700861 discloses the use of aqueous sulfurizing agents in alcohols for the synthesis of sulfur-containing alkoxysilanes. When different starting materials are used, large differences in the monomer content of the resulting polysulfurized alkoxysilanes are observed. A reliably consistent product quality can only be obtained on an industrial scale if the average length of the sulfur chains exceeds 3. Moreover, the use of four solid substances in the disclosed process is disadvantageous on an industrial scale.

[0004] WO 2008025580 A1 discloses a compound of the formula [R(R)(R'O)Si-R"-] 2 S m Preparation of sulfur-containing alkoxysilanes, wherein the alkali metal hydroxide content of all reactants is less than 0.44% by weight.

[0005] EP 2149579 discloses a process for preparing organosilanes of the general formula I by reacting (haloorganyl)alkoxysilanes of the formula II with aqueous alkali metal hydrogensulfide, sulfur and alkali metal carbonate in an alcohol.

[0006]

[0007] The molar ratio of the (halogenated organic) alkoxysilane of formula II to the alkali metal hydrogen sulfide is between 1:0.4 and 1:0.75, and the molar ratio of the alkali metal hydrogen sulfide to the alkali metal carbonate is between 1:0.5 and 1:1.5.

[0008] A disadvantage of the disclosed process is that, when sodium carbonate and / or sodium bicarbonate is used, the suspension obtained after the reaction can be very viscous, with the result that complete removal of the solvent and / or filtration is not possible using conventional apparatus (stirred tank reactors). Summary of the invention

[0009] The present invention provides a method for preparing a silane of formula II and one or more metal sulfides of formula III in an aqueous R by optionally adding y moles of sulfur in the presence of one or more salts of a monoprotic acid or a polyprotic acid, preferably a metal carbonate or a metal bicarbonate, more preferably sodium carbonate or sodium bicarbonate or a corresponding mixture thereof. 1 A method for preparing a polysulfur silane of formula I by reacting in a -OH solvent:

[0010] (R 1 O) 3-m R 2 m Si-R 3 -S x -R 3 -SiR 2 m (OR 1 ) 3-m I,

[0011] Where R 1 The same or different, and preferably CH 3 or C 2 H 5 C1-C10 alkyl, phenyl or alkyl polyether group -(R'-O) r -R″, wherein R′ is the same or different and is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C1-C30 hydrocarbon group, r is an integer from 1 to 30, and R″ is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group,

[0012] R 2 are the same or different and are C6-C20 aryl, C1-C10 alkyl, C2-C20 alkenyl, C7-C20 aralkyl or halogen,

[0013] R 3 are the same or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C1-C30 hydrocarbon groups,

[0014] and m is the same or different and is 0, 1, 2 or 3, preferably 0,

[0015] x is 1-10, preferably 2-4,

[0016] (R 1 O)3-m R 2 m Si-R 3 -Hal II

[0017] Where R 1 , R 2 , R 3 As defined above, and Hal is halogen, preferably chlorine or bromine, more preferably chlorine,

[0018] Me(SH) f and / or Me 3-f S x-y III

[0019] wherein Me is an element of the 1st or 2nd main group, preferably an element of the 1st main group, more preferably Na,

[0020] For Me of the first main group, f = 1, for Me of the second main group, f = 2,

[0021] and y has values ​​from 0 to x-1,

[0022] In the R 1 -OH solvent, R 1 As defined above,

[0023] Water-based R 1 The -OH solution has a water content of 5% to 40% by weight, preferably 5% to 15% by weight, and is characterized in that:

[0024] a. mixing a silane of formula II with one or more metal sulfides of formula III in an aqueous R optionally in the presence of one or more salts and optionally adding sulfur 1 The process stream from the reaction in the -OH solution is combined with the washing solution from step d,

[0025] The process stream comprises a polysulfur silane of formula I, a solvent R 1 -OH, water and process salts,

[0026] The washing solution comprises a solvent R 1 -OH, water and a polysulfur silane of formula I,

[0027] b. Removal of solvent R by distillation 1 -OH and water,

[0028] c. subjecting the remaining suspension comprising the polysulfur silane of formula I and the process salt to filtration or sedimentation, and

[0029] d. The process salt of step c is treated with solvent R 1 -OH washing, followed by drying,

[0030] The solvent R 1 The washing solution of -OH, water and polysulfur silane of the formula I is recycled to process step a.

[0031] The process of the present invention can be carried out continuously or batchwise, preferably batchwise.

[0032] When carried out as a batch process, the washing solution in process step a may originate from a previous batch of step d. When carried out as a batch process, the washing solution originating from process step d may be used in a subsequent batch of process step a.

[0033] The solvent R used in step d 1 The -OH may contain 0 to 20 wt %, preferably 2 to 10 wt % of water.

[0034] Process steps a and b can be carried out one after the other or in parallel.

[0035] The metal sulfides used may be present in anhydrous form, dissolved in water, or they may contain water of crystallization.

[0036] The sulphur used may be in granular, liquid or powder form.

[0037] The alkyl polyether group may be -(R'-O) r -R″

[0038] -(CH 2 -CH 2 O) 2 -C 8 H 17 、-(CH 2 -CH 2 O) 3 -C 8 H 17 、-(CH 2 -CH 2 O) 4 -C 8 H 17 、-(CH 2 -CH 2 O) 5 -C 8 H 17 、-(CH 2 -CH 2 O) 6 -C 8 H 17 、-(CH 2 -CH 2 O) 7 -C 8 H 17 ,

[0039] -(CH(CH 3 )-CH 2 O) 2 -C 8 H 17 、-(CH(CH 3 )-CH 2 O) 3 -C 8 H 17 、-(CH(CH 3 )-CH 2 O) 4 -C 8 H 17 、-(CH(CH 3 )-CH 2 O) 5 -C 8 H 17 、-(CH(CH 3 )-CH 2 O) 6 -C 8 H 17 、

[0040] -(CH(CH 3 )-CH 2 O) 7 -C 8 H 17 、

[0041] -(CH 2 -CH 2 O) 2 -C 9 H 19 、-(CH 2 -CH 2 O) 3 -C 9 H 19 、-(CH 2 -CH 2 O) 4 -C 9 H 19 、-(CH 2 -CH 2 O) 5 -C 9 H 19 、-(CH 2 -CH 2 O) 6 -C 9 H 19 、-(CH 2 -CH 2 O) 7 -C9 H 19 、

[0042] -(CH(CH 3 )-CH 2 O) 2 -C 9 H 19 、-(CH(CH 3 )-CH 2 O) 3 -C 9 H 19 、-(CH(CH 3 )-CH 2 O) 4 -C 9 H 19 、-(CH(CH 3 )-CH 2 O) 5 -C 9 H 19 、-(CH(CH 3 )-CH 2 O) 6 -C 9 H 19 、-(CH(CH 3 )-CH 2 O) 7 -C 9 H 19 、

[0043] -(CH 2 -CH 2 O) 2 -C 10 H 21 、-(CH 2 -CH 2 O) 3 -C 10 H 21 、-(CH 2 -CH 2 O) 4 -C 10 H 21 、-(CH 2 -CH 2 O) 5 -C 10 H 21 、-(CH 2 -CH 2 O) 6 -C 10 H 21 、-(CH 2 -CH 2 O)7 -C 10 H 21 、

[0044] -(CH(CH 3 )-CH 2 O) 2 -C 10 H 21 、-(CH(CH 3 )-CH 2 O) 3 -C 10 H 21 、-(CH(CH 3 )-CH 2 O) 4 -C 10 H 21 、-(CH(CH 3 )-CH 2 O) 5 -C 10 H 21 、-(CH(CH 3 )-CH 2 O) 6 -C 10 H 21 、-(CH(CH 3 )-CH 2 O) 7 -C 10 H 21 、

[0045] -(CH 2 -CH 2 O) 2 -C 11 H 23 、-(CH 2 -CH 2 O) 3 -C 11 H 23 、-(CH 2 -CH 2 O) 4 -C 11 H 23 、-(CH 2 -CH 2 O) 5 -C 11 H 23 、-(CH 2 -CH 2 O) 6 -C 11 H 23 、-(CH 2 -CH2 O) 7 -C 11 H 23 、

[0046] -(CH(CH 3 )-CH 2 O) 2 -C 11 H 23 、-(CH(CH 3 )-CH 2 O) 3 -C 11 H 23 、-(CH(CH 3 )-CH 2 O) 4 -C 11 H 23 、-(CH(CH 3 )-CH 2 O) 5 -C 11 H 23 、-(CH(CH 3 )-CH 2 O) 6 -C 11 H 23 、-(CH(CH 3 )-CH 2 O) 7 -C 11 H 23 、

[0047] -(CH 2 -CH 2 O) 2 -C 12 H 25 、-(CH 2 -CH 2 O) 3 -C 12 H 25 、-(CH 2 -CH 2 O) 4 -C 12 H 25 、-(CH 2 -CH 2 O) 5 -C 12 H 25 、-(CH 2 -CH 2 O) 6 -C 12 H 25 、-(CH2 -CH 2 O) 7 -C 12 H 25 、

[0048] -(CH(CH 3 )-CH 2 O) 2 -C 12 H 25 、-(CH(CH 3 )-CH 2 O) 3 -C 12 H 25 、-(CH(CH 3 )-CH 2 O) 4 -C 12 H 25 、-(CH(CH 3 )-CH 2 O) 5 -C 12 H 25 、-(CH(CH 3 )-CH 2 O) 6 -C 12 H 25 、-(CH(CH 3 )-CH 2 O) 7 -C 12 H 25 、

[0049] -(CH 2 -CH 2 O) 2 -C 13 H 27 、-(CH 2 -CH 2 O) 3 -C 13 H 27 、-(CH 2 -CH 2 O) 4 -C 13 H 27 、-(CH 2 -CH 2 O) 5 -C 13 H 27 、-(CH 2 -CH 2 O) 6 -C 13 H27 、-(CH 2 -CH 2 O) 7 -C 13 H 27 、

[0050] -(CH(CH 3 )-CH 2 O) 2 -C 13 H 27 、-(CH(CH 3 )-CH 2 O) 3 -C 13 H 27 、-(CH(CH 3 )-CH 2 O) 4 -C 13 H 27 、-(CH(CH 3 )-CH 2 O) 5 -C 13 H 27 、-(CH(CH 3 )-CH 2 O) 6 -C 13 H 27 、-(CH(CH 3 )-CH 2 O) 7 -C 13 H 27 、

[0051] -(CH 2 -CH 2 O) 2 -C 14 H 29 、-(CH 2 -CH 2 O) 3 -C 14 H 29 、-(CH 2 -CH 2 O) 4 -C 14 H 29 、-(CH 2 -CH 2 O) 5 -C 14 H 29 、-(CH 2 -CH 2 O) 6 -C14 H 29 、-(CH 2 -CH 2 O) 7 -C 14 H 29 、

[0052] -(CH(CH 3 )-CH 2 O) 2 -C 14 H 29 、-(CH(CH 3 )-CH 2 O) 3 -C 14 H 29 、-(CH(CH 3 )-CH 2 O) 4 -C 14 H 29 、-(CH(CH 3 )-CH 2 O) 5 -C 14 H 29 、-(CH(CH 3 )-CH 2 O) 6 -C 14 H 29 、-(CH(CH 3 )-CH 2 O) 7 -C 14 H 29 、

[0053] -(CH 2 -CH 2 O) 2 -C 15 H 31 、-(CH 2 -CH 2 O) 3 -C 15 H 31 、-(CH 2 -CH 2 O) 4 -C 15 H 31 、-(CH 2 -CH 2 O) 5 -C 15 H 31 、-(CH 2 -CH 2 O)6 -C 15 H 31 、-(CH 2 -CH 2 O) 7 -C 15 H 31 、

[0054] -(CH(CH 3 )-CH 2 O) 2 -C 15 H 31 、-(CH(CH 3 )-CH 2 O) 3 -C 15 H 31 、-(CH(CH 3 )-CH 2 O) 4 -C 15 H 31 、-(CH(CH 3 )-CH 2 O) 5 -C 15 H 31 、-(CH(CH 3 )-CH 2 O) 6 -C 15 H 31 、-(CH(CH 3 )-CH 2 O) 7 -C 15 H 31 、

[0055] -(CH 2 -CH 2 O) 2 -C 16 H 33 、-(CH 2 -CH 2 O) 3 -C 16 H 33 、-(CH 2 -CH 2 O) 4 -C 16 H 33 、-(CH 2 -CH 2 O) 5 -C 16 H 33 、-(CH 2 -CH2 O) 6 -C 16 H 33 、-(CH 2 -CH 2 O) 7 -C 16 H 33 、

[0056] -(CH(CH 3 )-CH 2 O) 2 -C 16 H 33 、-(CH(CH 3 )-CH 2 O) 3 -C 16 H 33 、-(CH(CH 3 )-CH 2 O) 4 -C 16 H 33 、-(CH(CH 3 )-CH 2 O) 5 -C 16 H 33 、-(CH(CH 3 )-CH 2 O) 6 -C 16 H 33 或-(CH(CH 3 )-CH 2 O) 7 -C 16 H 33 。

[0057] The polysulfide silane of formula I can be:

[0058] [(MeO) 3 Si(CH 2 ) 3 2 S、[(MeO) 3 Si(CH 2 ) 3 2 S 2 、[(MeO) 3 Si(CH 2 ) 3 2 S 3 、

[0059] [(MeO) 3 Si(CH​​​2 ) 3 ] 2 S 4 ,[(MeO) 3 Si(CH 2 ) 3 ] 2 S 5 ,[(MeO) 3 Si(CH 2 ) 3 ] 2 S 6 、

[0060] [(MeO) 3 Si(CH 2 ) 3 ] 2 S 7 ,[(MeO) 3 Si(CH 2 ) 3 ] 2 S 8 ,[(MeO) 3 Si(CH 2 ) 3 ] 2 S 9 、

[0061] [(MeO) 3 Si(CH 2 ) 3 ] 2 S 10 、

[0062] [(EtO) 3 Si(CH 2 ) 3 ] 2 S[(EtO) 3 Si(CH 2 ) 3 ] 2 S 2 ,[(EtO) 3 Si(CH 2 ) 3 ] 2 S 3 、

[0063] [(EtO) 3 Si(CH 2 ) 3 ] 2 S 4 ,[(EtO) 3 Si(CH 2 ) 3 ]2 S 5 ,[(EtO) 3 Si(CH 2 ) 3 ] 2 S 6 、

[0064] [(EtO) 3 Si(CH 2 ) 3 ] 2 S 7 ,[(EtO) 3 Si(CH 2 ) 3 ] 2 S 8 ,[(EtO) 3 Si(CH 2 ) 3 ] 2 S 9 、

[0065] [(EtO) 3 Si(CH 2 ) 3 ] 2 S 10 、

[0066] [(C 3 H 7 O) 3 Si(CH 2 ) 3 ] 2 S[(C 3 H 7 O) 3 Si(CH 2 ) 3 ] 2 S 2 ,[(C 3 H 7 O) 3 Si(CH 2 ) 3 ] 2 S 3 、

[0067] [(C 3 H 7 O) 3 Si(CH 2 ) 3 ] 2 S 4 ,[(C 3 H 7 O) 3 Si(CH2 ) 3 ] 2 S 5 ,

[0068] [(C 3 H 7 O) 3 Si(CH 2 ) 3 ] 2 S 6 、[(C 3 H 7 O) 3 Si(CH 2 ) 3 ] 2 S 7 ,

[0069] [(C 3 H 7 O) 3 Si(CH 2 ) 3 ] 2 S 8 、[(C 3 H 7 O) 3 Si(CH 2 ) 3 ] 2 S 9 ,

[0070] [(C 3 H 7 O) 3 Si(CH 2 ) 3 ] 2 S 10 .

[0071] The following compounds are preferably used as silanes of the formula II:

[0072] 3-Chlorobutyl (triethoxysilane), 3-chlorobutyl (trimethoxysilane), 3-chlorobutyl (diethoxymethoxysilane), 3-chloropropyl (triethoxysilane), 3-chloropropyl (trimethoxysilane), 3-chloropropyl (diethoxymethoxysilane), 2-chloroethyl (triethoxysilane), 2-chloroethyl (trimethoxysilane), 2-chloroethyl (diethoxymethoxysilane), 1-chloromethyl (triethoxysilane), 1-chloromethyl (trimethoxysilane), 1-chloromethyl (diethoxymethoxysilane), 3-chloropropyl ( Diethoxymethylsilane), 3-chloropropyl(dimethoxymethylsilane), 2-chloroethyl(diethoxymethylsilane), 2-chloroethyl(dimethoxymethylsilane), 1-chloromethyl(diethoxymethylsilane), 1-chloromethyl(dimethoxymethylsilane), 3-chloropropyl(ethoxydimethylsilane), 3-chloropropyl(methoxydimethylsilane), 2-chloroethyl(ethoxydimethylsilane), 2-chloroethyl(methoxydimethylsilane), 1-chloromethyl(ethoxydimethylsilane), 1-chloromethyl(methoxydimethylsilane),

[0073] [(C 9 H 19 O-(CH 2 -CH 2 O) 2 ](MeO) 2 Si(CH 2 ) 3 Cl,

[0074] [(C 9 H 19 O-(CH 2 -CH 2 O) 3 ](MeO) 2 Si(CH 2 ) 3 Cl,

[0075] [(C 9 H 19 O-(CH 2 -CH 2 O) 4 ](MeO) 2 Si(CH 2 ) 3 Cl,

[0076] [(C 9 H 19 O-(CH 2 -CH 2 O) 5 ](MeO) 2 Si(CH 2 )3 Cl、

[0077] [(C 9 H 19 O-(CH 2 -CH 2 Oh) 6 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0078] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 2 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0079] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 3 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0080] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 4 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0081] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 5 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0082] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 6 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0083] [(C13 H 27 O-(CH 2 -CH 2 Oh) 2 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0084] [(C 13 H 27 O-(CH 2 -CH 2 Oh) 3 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0085] [(C 13 H 27 O-(CH 2 -CH 2 Oh) 4 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0086] [(C 13 H 27 O-(CH 2 -CH 2 Oh) 5 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0087] [(C 13 H 27 O-(CH 2 -CH 2 Oh) 6 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0088] [(C 14 H 29 O-(CH 2 -CH 2 Oh) 2 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0089] [(C 14 H 29 O-(CH 2 -CH2 Oh) 3 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0090] [(C 14 H 29 O-(CH 2 -CH 2 Oh) 4 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0091] [(C 14 H 29 O-(CH 2 -CH 2 Oh) 5 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0092] [(C 14 H 29 O-(CH 2 -CH 2 Oh) 6 ](MeO) 2 Si(CH 2 ) 3 Cl、

[0093] [(C 9 H 19 O-(CH 2 -CH 2 Oh) 2 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0094] [(C 9 H 19 O-(CH 2 -CH 2 Oh) 3 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0095] [(C 9 H 19 O-(CH 2 -CH 2 Oh) 4 ] 2(MeO)Si(CH 2 ) 3 Cl、

[0096] [(C 9 H 19 O-(CH 2 -CH 2 Oh) 5 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0097] [(C 9 H 19 O-(CH 2 -CH 2 Oh) 6 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0098] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 2 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0099] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 3 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0100] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 4 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0101] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 5 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0102] [(C 12 H 25 O-(CH 2 -CH 2 Oh) 6 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0103] [(C 13 H 27 O-(CH 2 -CH 2 Oh) 2 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0104] [(C 13 H 27 O-(CH 2 -CH 2 Oh) 3 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0105] [(C 13 H 27 O-(CH 2 -CH 2 Oh) 4 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0106] [(C 13 H 27 O-(CH 2 -CH 2 Oh) 5 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0107] [(C 13 H 27 O-(CH 2 -CH 2 Oh) 6 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0108] [(C 14 H29 O-(CH 2 -CH 2 Oh) 2 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0109] [(C 14 H 29 O-(CH 2 -CH 2 Oh) 3 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0110] [(C 14 H 29 O-(CH 2 -CH 2 Oh) 4 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0111] [(C 14 H 29 O-(CH 2 -CH 2 Oh) 5 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0112] [(C 14 H 29 O-(CH 2 -CH 2 Oh) 6 ] 2 (MeO)Si(CH 2 ) 3 Cl、

[0113] [(C 9 H 19 O-(CH 2 -CH 2 Oh) 2 ](EtO) 2 Si(CH 2 ) 3 Cl、

[0114] [(C 9 H 19 O-(CH 2 -CH 2 Oh)3 ](EtO) 2 Si(CH 2 ) 3 Cl、

[0115] [(C 9 H 19 O-(CH 2 -CH 2 O) 4 ](EtO) 2 Si(CH 2 ) 3 Cl、

[0116] [(C 9 H 19 O-(CH 2 -CH 2 O) 5 ](EtO) 2 Si(CH 2 ) 3 Cl、

[0117] [(C 9 H 19 O-(CH 2 -CH 2 O) 6 ](EtO) 2 Si(CH 2 ) 3 Cl、

[0118] [(C 12 H 25 O-(CH 2 -CH 2 O) 2 ](EtO) 2 Si(CH 2 ) 3 Cl、

[0119] [(C 12 H 25 O-(CH 2 -CH 2 O) 3 ](EtO) 2 Si(CH 2 ) 3 Cl、

[0120] [(C 12 H 25 O-(CH 2 -CH 2 O) 4 ](EtO) 2 Si(CH 2) 3 Cl

[0121] [(C 12 H 25 O-(CH 2 -CH 2 O) 5 ](EtO) 2 Si(CH 2 ) 3 Cl

[0122] [(C 12 H 25 O-(CH 2 -CH 2 O) 6 ](EtO) 2 Si(CH 2 ) 3 Cl

[0123] [(C 13 H 27 O-(CH 2 -CH 2 O) 2 ](EtO) 2 Si(CH 2 ) 3 Cl

[0124] [(C 13 H 27 O-(CH 2 -CH 2 O) 3 ](EtO) 2 Si(CH 2 ) 3 Cl

[0125] [(C 13 H 27 O-(CH 2 -CH 2 O) 4 ](EtO) 2 Si(CH 2 ) 3 Cl

[0126] [(C 13 H 27 O-(CH 2 -CH 2 O) 5 ](EtO) 2 Si(CH 2 ) 3 Cl

[0127] [(C13 H 27 O-(CH 2 -CH 2 O) 6 ](EtO) 2 Si(CH 2 ) 3 Cl

[0128] [(C 14 H 29 O-(CH 2 -CH 2 O) 2 ](EtO) 2 Si(CH 2 ) 3 Cl

[0129] [(C 14 H 29 O-(CH 2 -CH 2 O) 3 ](EtO) 2 Si(CH 2 ) 3 Cl

[0130] [(C 14 H 29 O-(CH 2 -CH 2 O) 4 ](EtO) 2 Si(CH 2 ) 3 Cl

[0131] [(C 14 H 29 O-(CH 2 -CH 2 O) 5 ](EtO) 2 Si(CH 2 ) 3 Cl

[0132] [(C 14 H 29 O-(CH 2 -CH 2 O) 6 ](EtO) 2 Si(CH 2 ) 3 Cl

[0133] [(C 9 H 19 O-(CH 2 -CH2 O) 2 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0134] [(C 9 H 19 O-(CH 2 -CH 2 O) 3 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0135] [(C 9 H 19 O-(CH 2 -CH 2 O) 4 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0136] [(C 9 H 19 O-(CH 2 -CH 2 O) 5 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0137] [(C 9 H 19 O-(CH 2 -CH 2 O) 6 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0138] [(C 12 H 25 O-(CH 2 -CH 2 O) 2 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0139] [(C 12 H 25 O-(CH 2 -CH 2 O) 3 ] 2(EtO)Si(CH 2 ) 3 Cl

[0140] [(C 12 H 25 O-(CH 2 -CH 2 O) 4 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0141] [(C 12 H 25 O-(CH 2 -CH 2 O) 5 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0142] [(C 12 H 25 O-(CH 2 -CH 2 O) 6 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0143] [(C 13 H 27 O-(CH 2 -CH 2 O) 2 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0144] [(C 13 H 27 O-(CH 2 -CH 2 O) 3 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0145] [(C 13 H 27 O-(CH 2 -CH 2 O) 4 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0146] [(C 13 H 27 O-(CH 2 -CH 2 O) 5 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0147] [(C 13 H 27 O-(CH 2 -CH 2 O) 6 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0148] [(C 14 H 29 O-(CH 2 -CH 2 O) 2 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0149] [(C 14 H 29 O-(CH 2 -CH 2 O) 3 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0150] [(C 14 H 29 O-(CH 2 -CH 2 O) 4 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0151] [(C 14 H 29 O-(CH 2 -CH 2 O) 5 ] 2 (EtO)Si(CH 2 ) 3 Cl

[0152] [(C 14 H29 O-(CH 2 -CH 2 O) 6 ] 2 (EtO)Si(CH 2 ) 3 Cl、

[0153] [(C 9 H 19 O-(CH 2 -CH 2 O) 2 ] 3 Si(CH 2 ) 3 Cl、

[0154] [(C 9 H 19 O-(CH 2 -CH 2 O) 3 ] 3 Si(CH 2 ) 3 Cl、

[0155] [(C 9 H 19 O-(CH 2 -CH 2 O) 4 ] 3 Si(CH 2 ) 3 Cl、

[0156] [(C 9 H 19 O-(CH 2 -CH 2 O) 5 ] 3 Si(CH 2 ) 3 Cl、

[0157] [(C 9 H 19 O-(CH 2 -CH 2 O) 6 ] 3 Si(CH 2 ) 3 Cl、

[0158] [(C 12 H 25 O-(CH 2 -CH 2 O) 2 ] 3Si(CH 2 ) 3 Cl、

[0159] [(C 12 H 25 O-(CH 2 -CH 2 O) 3 ] 3 Si(CH 2 ) 3 Cl、

[0160] [(C 12 H 25 O-(CH 2 -CH 2 O) 4 ] 3 Si(CH 2 ) 3 Cl、

[0161] [(C 12 H 25 O-(CH 2 -CH 2 O) 5 ] 3 Si(CH 2 ) 3 Cl、

[0162] [(C 12 H 25 O-(CH 2 -CH 2 O) 6 ] 3 Si(CH 2 ) 3 Cl、

[0163] [(C 13 H 27 O-(CH 2 -CH 2 O) 2 ] 3 Si(CH 2 ) 3 Cl、

[0164] [(C 13 H 27 O-(CH 2 -CH 2 O) 3 ] 3 Si(CH 2 ) 3 Cl、

[0165] [(C 13H 27 O-(CH 2 -CH 2 O) 4 ] 3 Si(CH 2 ) 3 Cl、

[0166] [(C 13 H 27 O-(CH 2 -CH 2 O) 5 ] 3 Si(CH 2 ) 3 Cl、

[0167] [(C 13 H 27 O-(CH 2 -CH 2 O) 6 ] 3 Si(CH 2 ) 3 Cl、

[0168] [(C 14 H 29 O-(CH 2 -CH 2 O) 2 ] 3 Si(CH 2 ) 3 Cl、

[0169] [(C 14 H 29 O-(CH 2 -CH 2 O) 3 ] 3 Si(CH 2 ) 3 Cl、

[0170] [(C 14 H 29 O-(CH 2 -CH 2 O) 4 ] 3 Si(CH 2 ) 3 Cl、

[0171] [(C 14 H 29 O-(CH 2 -CH 2 O) 5 ] 3Si(CH 2 ) 3 Cl or

[0172] [(C 14 H 29 O-(CH 2 -CH 2 O) 6 ] 3 Si(CH 2 ) 3 Cl.

[0173] The method can be carried out at a temperature of 0°C to 180°C, preferably at a temperature of 30°C to 150°C, more preferably at a temperature of 50°C to 100°C, particularly preferably at a temperature of 60°C to 90°C.

[0174] Reaction of a silane of formula II with one or more metal sulfides of formula III:

[0175] The reaction of the silane of formula II with one or more metal sulfides of formula III can be carried out in any metering sequence; after metering in the other starting materials, the metal sulfide or metal hydrogensulfide or the silane of formula II is preferably added in portions or at a uniform rate over a period of 0.1 to 10 hours, preferably 0.5 to 2 hours, for temperature control.

[0176] The metal sulfide of formula III, the optional sulfur, the optional metal carbonate / metal bicarbonate, and the solvent may be premixed in whole or in part prior to the reaction.

[0177] The haloalkylalkoxysilane of formula II, the optional sulfur, the optional metal carbonate / metal bicarbonate, and the solvent may be combined or premixed in whole or in part prior to the reaction.

[0178] Premixing can be performed inside or outside the reaction chamber.

[0179] The molar ratio between the metal sulfide of formula III and the silane of formula II used may be in the range of 0.2 to 2, preferably between 0.4 and 1, more preferably between 0.4 and 0.7.

[0180] The molar ratio between the metal hydrogensulfide and the metal carbonate used may be between 0.5 and 2, preferably between 0.8 and 1.2.

[0181] Solvent R used 1 The molar ratio between -OH and the silane of the formula II used can be from 0.5 to 100, preferably from 1 to 20, more preferably from 2 to 5.

[0182] Solvent R 1The -OH may contain 0 to 20 wt %, preferably 2 to 10 wt % of water.

[0183] The product-wetted parts of the apparatus for carrying out the invention can be made of metal, plastic, ceramic or glass. Preference is given to using apparatus made of corrosion-resistant materials, such as enameled or plastic-coated steel or steel alloys. Particular preference is given to using apparatus made of enameled steel, stainless steel, duplex steel, tantalum or Hastelloy.

[0184] The reaction can be carried out in a reaction tube or a reaction tank, preferably in a reaction tank. The method according to the present invention can be carried out in an open or closed container. Preferably, the reaction is carried out in a closed container.

[0185] The mixing of the reactor contents can be carried out by internal or external circulation. The reaction apparatus can be heated and / or cooled. The heat of reaction can be removed by direct or indirect cooling. The heat of reaction can be removed by evaporative cooling. Evaporative cooling can be carried out using the solvent present in the process. The reaction is preferably carried out in a stirred tank reactor heated and cooled by a half-pipe coil or jacket. The reaction can be carried out in a closed system. Before adding the individual raw materials, the reactor can be evacuated. It is particularly advantageous to evacuate before metering the silane of formula II and the metal sulfide or metal hydrogensulfide. Very preferably, the reaction vessel can be evacuated before adding the metal sulfide or metal hydrogensulfide. The method according to the invention can be carried out in such a way that the generated gas cannot escape from the reaction chamber. The closed container can preferably be a reaction vessel known in the prior art, which allows operation at a pressure of 10Pa to 2MPa and a temperature of 0°C to 200°C. The closed container can particularly preferably be a reaction vessel known in the prior art, which allows operation at a pressure of 10Pa to 1.2MPa and a temperature of 0°C to 150°C.

[0186] Method step a:

[0187] The merging of the process stream from the reaction of the silane of formula II with one or more metal sulfides of formula III with the washing solution from step d in method step a of the method can be carried out after or before the reaction of the silane of formula II with one or more metal sulfides of formula III is completed. The merging can be carried out inside or outside the container used for the reaction. The merging can be carried out inside the container used for distillation. The merging can be carried out before or during the distillation process (method step b).

[0188] Method step b:

[0189] The removal of the solvent by distillation in method step b can be carried out in a stirred tank reactor. The stirred tank reactor can also be a reaction unit. The removal of the solvent by distillation can be carried out in a temperature range of 0°C to 150°C, at an absolute pressure of 0.5 kPa to an absolute pressure of 150 kPa, preferably in a range of 40°C to 120°C, at an absolute pressure of 0.5°C to an absolute pressure of 30 kPa. In the process of removing the solvent by distillation, the pressure in the distillation apparatus can be reduced in a stepwise manner or continuously reduced. The evaporated solvent can be purified or concentrated immediately or subsequently after its evaporation. During the evaporation, the contents of the distillation apparatus can be mixed. The mixing can be carried out in an appropriate manner internally or externally. Examples of suitable mixing means are a stirrer unit, a circulating pump, or by blowing a gas or evaporated liquid, in particular steam, through the mixture.

[0190] Method step c:

[0191] The removal of solids in method step c can be carried out in various filtering and settling machines. The removal of solids can be carried out continuously or intermittently. Filters that can be used are filter centrifuges, filter presses or filter dryers. Settling machines that can be used are rotary drum settling centrifuges. During the filtering process, it may be helpful to compensate for the shrinkage of the filter cake volume by smoothing or compressing the filter cake. Particularly suitable for this purpose are the plough units of filter dryers.

[0192] Method step d:

[0193] The washing of the solid in process step d can be carried out inside or outside the plant components used in the preceding process step. The washing can be carried out continuously or intermittently. During the washing, the solid to be washed can be mixed with the solvent R in a suitable manner. 1 -OH mixing. The separation between the washing solution and the washed solid can be carried out by precipitation or by filtration. A rotary drum sedimentation centrifuge, a filter dryer, a filter press and a filter centrifuge can be used to separate the washed solid from the washing solution. The washing of the obtained filter cake is preferably carried out in a filter dryer.

[0194] The drying of the solid in method step d can be carried out inside or outside the assembly for washing the solid. Drying can be carried out intermittently or continuously. Drying can be carried out at a temperature of 0° C. to 150° C., preferably 40° C. to 100° C. The pressure during drying can be 0.1 kPa absolute pressure to 150 kPa absolute pressure, preferably 1 kPa absolute pressure to 102 kPa absolute pressure. During the drying process, the pressure can be reduced and / or the temperature can be increased. Gas can be used for drying. Nitrogen or air are particularly suitable. The drying of the solid can preferably be carried out in a filter dryer.

[0195] Process steps c and d can be carried out in the same apparatus.

[0196] Wetting agents can be added before or during individual method steps.

[0197] An advantage of the process according to the invention is the complete removal of the solvent from the suspension, which is made possible by providing a sufficient amount of liquid to keep the mixture stirrable and movable during the distillation process. Another advantage is that the suspension can be better handled after the distillation is over. Also advantageous are the increased yields obtained by the process according to the invention and the increased monomer content. Examples:

[0198] The average sulfur chain length is determined by the analytical method described in ASTM D 6844.

[0199] To determine the monomer content, the peak areas of sample components S2 to S10 are multiplied by the response factors listed in ASTM D 6844 and their sum is related to the sum of the peak areas S2 to S10 of the calibrated response factors of a standard of known monomer content according to the following formula:

[0200] DETAILED DESCRIPTION

[0201] Embodiment 1 (comparative example):

[0202] 477 g of ethanol, 53 g of water, 137.2 g of sodium carbonate, 38.6 g of sulfur and 109.2 g of sodium hydrosulfide having a water content of 29% are weighed into a pressure reactor having a capacity of 2000 ml. The reactor is closed and evacuated to an absolute pressure of 10 kPa. The reactor contents are then heated to 70° C. with stirring and 554.5 g of chloropropyltriethoxysilane are added within 45 minutes at a temperature of 70° C. to 73° C. The reactor contents are then heated to 78° C. and maintained at this temperature for a further 145 minutes.

[0203] After the reactor contents had been cooled to 45° C., the removal of the ethanol-water mixture from the suspension remaining in the reactor under reduced pressure was started. Upon reaching a temperature of 120° C., the suspension present in the reactor was cooled to 30° C. The reactor was opened and its pasty contents were transferred to a ceramic suction filter. After filtering under vacuum for one hour, 323.9 g of a bis(triethoxysilylpropyl)polysulfane product having an average sulfur chain length of 2.16 and a monomer content of 80.3% were obtained.

[0204] The filter cake from Example 1 remaining in the ceramic suction filter was then washed with a mixture of 477 g of ethanol and 53 g of water, under applied vacuum. After 60 minutes, 542 g of washing solution were obtained.

[0205] Embodiment 2:

[0206] 477 g of ethanol, 53 g of water, 137.2 g of sodium carbonate, 38.6 g of sulfur and 109.2 g of sodium hydrosulfide having a water content of 29% are weighed into a pressure reactor having a capacity of 2000 ml. The reactor is closed and evacuated to an absolute pressure of 10 kPa. The reactor contents are then heated to 70° C. with stirring and 554.5 g of chloropropyltriethoxysilane are added within 45 minutes at a temperature of 70° C. to 73° C. The reactor contents are then heated to 78° C. and maintained at this temperature for a further 145 minutes.

[0207] After the reactor contents had been cooled to 45° C., the removal of the ethanol-water mixture from the suspension remaining in the reactor under reduced pressure was started. Once 250 g of distillate had been collected, a washing solution previously obtained by washing the filter cake obtained in Example 1 was added and the distillation was continued. On reaching a temperature of 120° C., the suspension present in the reactor was cooled to 30° C. The viscosity of the reactor contents was low enough to make it possible to transfer the suspension through the bottom outlet of the reactor to a ceramic suction filter.

[0208] After filtering under vacuum for one hour, 525.7 g of a bis(triethoxysilylpropyl)polysulfane product having an average sulfur chain length of 2.14 and a monomer content of 86.0% was obtained.

Claims

1. A method of reacting a silane of formula II with one or more metal sulfides of formula III in an aqueous R, optionally in the presence of one or more salts of a monoprotic acid or a polyprotic acid, optionally with the addition of y moles of sulfur. 1 A method for preparing a polysulfur silane of formula I by reaction in a -OH solvent: (R 1 O) 3-m R 2 m Si-R 3 -S x -R 3 -SiR 2 m (OR 1 ) 3-m I, Where R 1 are the same or different and are C1-C10 alkyl, R 2 are the same or different and are C1-C10 alkyl, R 3 are the same or different and are branched or unbranched, saturated, aliphatic divalent C1-C30 hydrocarbon groups, m are the same or different and are 0, 1, 2 or 3, x is 1-10, (R 1 o) 3-m R 2 m Si-R 3 - Hall II Where R 1 , R 2 , R 3 and m are as defined above, and Hal is halogen, Me(SH) f III Where Me is an element of the 1st or 2nd main group, For Me of the first main group, f = 1, for Me of the second main group, f = 2, and y has values ​​from 0 to x-1, In the aqueous R 1 -OH solvent, R1 is as defined above, The aqueous R 1 The water content of the -OH solution is 5% to 40% by weight, characterized in that a. in the presence of one or more salts and optionally under the conditions of adding sulfur, the silane of formula II and one or more metal sulfides of formula III in aqueous R 1 The process stream from the reaction in the -OH solution is combined with the washing solution from step d, The process stream comprises a polysulfur silane of formula I, a solvent R 1 -OH, water and process salts, The washing solution comprises a solvent R 1 -OH, water and a polysulfur silane of formula I, b. Removal of solvent R by distillation 1 -OH and water, c. subjecting the remaining suspension comprising the polysulfur silane of formula I and the process salt to filtration or sedimentation, and d. The process salt of step c is treated with solvent R 1 -OH washing, followed by drying, and the solvent R 1 The scrubbing solution of -OH, water and polysulfur silane of the formula I is recycled to process step a.

2. The method for preparing a polysulfur silane of formula I according to claim 1, characterized in that: The process is carried out at a temperature of 0°C to 180°C.

3. The method for preparing polysulfur silane of formula I according to claim 1, characterized in that: The polysulfur silane of formula I is [(EtO)3Si(CH2)3]2S, [(EtO)3Si(CH2)3]2S2, [(EtO)3Si(CH2)3]2S3, [(EtO)3Si(CH2)3]2S4, [(EtO)3Si(CH2)3]2S5, [(EtO)3Si(CH2)3]2S6, [(EtO)3Si(CH2)3]2S7, [(EtO)3Si(CH2)3]2S8, [(EtO)3Si(CH2)3]2S9 or [(EtO)3Si(CH2)3]2S 10 .

4. The method for preparing polysulfur silane of formula I according to claim 1, characterized in that: The method steps a and b are carried out in parallel.

5. The method for preparing polysulfur silane of formula I according to claim 1, characterized in that: The process is carried out continuously or batchwise.

6. The method for preparing polysulfur silane of formula I according to claim 1, characterized in that: If carried out in batch operation, the washing solution in process step a originates from step d of the preceding batch.

7. The method for preparing polysulfur silane of formula I according to claim 1, characterized in that: In process step d., the washed solids can be separated from the washing solution using a drum decanter centrifuge, a filter dryer, a filter press or a filter centrifuge.

8. The method for preparing polysulfur silane of formula I according to claim 1, characterized in that: The removal of the solvent by distillation in process step b is carried out in a temperature range of 0° C. to 150° C. and at a pressure of 0.5 kPa absolute to 150 kPa absolute.

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