Method for preparing polysulfane silane by phase transfer catalysis

Abstract

The present invention relates to a method for preparing polysulfanesilane of formula I (R 1 ) 3‑m R 2 m Si‑R 3 ‑S x ‑R 3 ‑SiR 2 m (R 1 ) 3‑m I is to react at least one silane (R 1 ) 3‑m R 2 m Si‑R 3 ‑Hal II and M(SH) y and / or M z S and sulfur are reacted, wherein at least one carrier steam distillation and / or ozone treatment is performed during or after the reaction.

Description

[0001] The present invention provides a method for preparing polysulfane silane by phase transfer catalysis.

[0002] US 5,405,985, US 5,583,245 and US 5,663,396 disclose the preparation of Z-Alk-S by phase transfer catalysis. n -Alk-Z compounds.

[0003] US Pat. No. 5,468,893 also discloses the preparation of polysulfanesilanes by phase transfer catalysis in the presence of alkali metal halides or alkali metal sulfates.

[0004] US 6,384,255 and US 6,448,426 disclose changes in the order of addition of phase transfer catalysis.

[0005] In US 6,384,256, M2S is reacted in the presence of MOH in a preliminary reaction. n Or MSH reacts with sulfur.

[0006] US 6,740,767 and US 6,534,668 also disclose the addition of a buffer in phase transfer catalysis.

[0007] Handbook of Phase Transfer Catalysis (ISBN 978-0-7514-0258-2), Chapter 3, pages 123-127 discloses the decomposition of quaternary ammonium phase transfer catalysts, such as the decomposition of tert-butylammonium bromide to tributylamine.

[0008] A disadvantage of the known PTC processes for preparing polysulfanesilanes is that degradation products of the catalyst in the end product are sometimes toxic or harmful to health.

[0009] The present invention provides a method for preparing polysulfane silane of formula I

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

[0011] Where R 1 Identical or different and are C1-C10-alkoxy, phenoxy or alkyl polyether groups -(R'-O) rR", wherein R' is identical or different and is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C1-C30 hydrocarbon radical, r is an integer from 1 to 30 and R" is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl radical,

[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 the same or different and branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C1-C30 hydrocarbon radicals,

[0014] and m is the same or different and is 0, 1, 2 or 3, x is 2-10, preferably 2-4,

[0015] The method is to prepare a phase transfer catalyst of formula III in the presence of a base, an aqueous phase and a phase transfer catalyst of formula III.

[0016]

[0017] wherein Y is an element of the 5th main group, preferably N, P or As, more preferably N or P, most preferably N,

[0018] R 4 , R 5 , R 6 and R 7 The same or different and are -(CH2) k CH3 alkyl, wherein k = 0-9, or in the group consisting of R 4 , R 5 , R 6 and R 7 There is one or two ring closures between the two substituents of the group -(CH2) n -, wherein n = 2-5, preferably n = 4, and X - F - ,I - , Cl - Br - 、ClO4 - PF6 - 、BF4 - 、(C6H5)4B - 、H2PO4 - 、CH3SO3 - 、C6H5SO3 - 、HSO4 - 、NO3 - or 1 / 2SO4 2- ,

[0019] At least one silane of formula II

[0020] (R 1 ) 3-m R 2 m Si-R 3 -Hal II

[0021] wherein Hal is Cl, Br or I, preferably Cl,

[0022] and M(SH) y (preferably NaSH) and / or M z S (preferably Na2S) and / or M g S h and / or sulfur reaction,

[0023] Where y = 1 or 2, when y = 1, M = Na or K, when y = 2, M = Ca or Mg, and

[0024] z=1 or 2, when z=1, M=Ca or Mg, when z=2, M=Na or K, and

[0025] g=1 or 2, when g=1, M=Ca or Mg, when g=2, M=Na or K,

[0026] h = a natural number from 1 to 10,

[0027] The method is characterized in that at least one carrier steam distillation and / or ozone treatment is carried out during or after the reaction.

[0028] The following situation can be preferred: R 1 is ethoxy, m=0 and R 3 =(CH2)3.

[0029] The situation where Hal=Cl is preferred.

[0030] The polysulfanesilane of formula I may preferably be: [(CH3O)3Si(CH2)3]2S, [(CH3O)3Si(CH2)3]2S2, [(CH3O)3Si(CH2)3]2S3, [(CH3O)3Si(CH2)3]2S4, [(CH3O)3Si(CH2)3]2S5, [(CH3O)3Si(CH2)3]2S6, [(CH3O)3Si(CH2)3]2S7, [(CH3O)3Si(CH2)3]2S8, [(CH3O)3Si(CH2)3]2S9, [(CH3O)3Si(CH2)3]2S 10 、[(CH3O)3Si(CH2)3]2S 11<h2 style=";text-align:left;direction:ltr">[(CH3O)3Si(CH2)3]2S<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> 、[(CH3CH2O)3Si(CH2)3]2S、[(CH3CH2O)3Si(CH2)3]2S2、[(CH3CH2O)3Si(CH2)3]2S3、[(CH3CH2O)3Si(CH2)3]2S4、[(CH3CH2O)3Si(CH2)3]2S5、[(CH3CH2O)3Si(CH2)3]2S6、[(CH3CH2O)3Si(CH2)3]2S7、[(CH3CH2O)3Si(CH2)3]2S8、[(CH3CH2O)3Si(CH2)3]2S9、[(CH3CH2O)3Si(CH2)3]2S<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> [(CH3CH2O)3Si(CH2)3]2S<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> [(CH3CH2O)3Si(CH2)3]2S<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> 、[(C3H7O)3Si(CH2)3]2S、[(C3H7O)3Si(CH2)3]2S2、[(C3H7O)3Si(CH2)3]2S3、[(C3H7O)3Si(CH2)3]2S4、[(C3H7O)3Si(CH2)3]2S5、[(C3H7O)3Si(CH2)3]2S6、[(C3H7O)3Si(CH2)3]2S7、[(C3H7O)3Si(CH2)3]2S8、[(C3H7O)3Si(CH2)3]2S9、[(C3H7O)3Si(CH2)3]2S<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> [(C3H7O)3Si(CH2)3]2S<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> [(C3H7O)3Si(CH2)3]2S<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> 。<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0031] The silanes of formula II used may preferably be: 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), [(C9H 19 O-(CH2-CH2O)2](CH3O)2Si(CH2)3Cl, [(C9H 19 O-(CH2-CH2O)3](CH3O)2Si(CH2)3Cl, [(C9H 19 O-(CH2-CH2O)4](CH3O)2Si(CH2)3Cl, [(C9H 19 O-(CH2-CH2O)5](CH3O)2Si(CH2)3Cl, [(C9H 19 O-(CH2-CH2O)6](CH3O)2Si(CH2)3Cl, [(C 12 H 25 O-(CH2-CH2O)2](CH3O)2Si(CH2)3Cl, [(C 12 H 25 O-(CH2-CH2O)3](CH3O)2Si(CH2)3Cl, [(C 12 H 25 O-(CH2-CH2O)4](CH3O)2Si(CH2)3Cl, [(C 12 H 25 O-(CH2-CH2O)5](CH3O)2Si(CH2)3Cl, [(C 12 H 25 O-(CH2-CH2O)6](CH3O)2Si(CH2)3Cl, [(C 13 H 27O-(CH2-CH2O)2](CH3O)2Si(CH2)3Cl [(C 13 H 27 O-(CH2-CH2O)3](CH3O)2Si(CH2)3Cl [(C 13 H 27 O-(CH2-CH2O)4](CH3O)2Si(CH2)3Cl [(C 13 H 27 O-(CH2-CH2O)5](CH3O)2Si(CH2)3Cl [(C 13 H 27 O-(CH2-CH2O)6](CH3O)2Si(CH2)3Cl [(C 14 H 29 O-(CH2-CH2O)2](CH3O)2Si(CH2)3Cl [(C 14 H 29 O-(CH2-CH2O)3](CH3O)2Si(CH2)3Cl [(C 14 H 29 O-(CH2-CH2O)4](CH3O)2Si(CH2)3Cl [(C 14 H 29 O-(CH2-CH2O)5](CH3O)2Si(CH2)3Cl [(C 14 H 29 O-(CH2-CH2O)6](CH3O)2Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)2]2(CH3O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)3]2(CH3O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)4]2(CH3O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)5]2(CH3O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)6]2(CH3O)Si(CH2)3Cl,[(C 12 H 25 O-(CH2-CH2O)2]2(CH3O)Si(CH2)3Cl,[(C 12 H 25 O-(CH2-CH2O)3]2(CH3O)Si(CH2)3Cl,[(C 12 H 25O-(CH2-CH2O)4]2(CH3O)Si(CH2)3Cl,[(C 12 H 25 O-(CH2-CH2O)5]2(CH3O)Si(CH2)3Cl,[(C 12 H 25 O-(CH2-CH2O)6]2(CH3O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)2]2(CH3O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)3]2(CH3O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)4]2(CH3O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)5]2(CH3O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)6]2(CH3O)Si(CH2)3Cl,[(C 14 H 29 O-(CH2-CH2O)2]2(CH3O)Si(CH2)3Cl,[(C 14 H 29 O-(CH2-CH2O)3]2(CH3O)Si(CH2)3Cl,[(C 14 H 29 O-(CH2-CH2O)4]2(CH3O)Si(CH2)3Cl,[(C 14 H 29 O-(CH2-CH2O)5]2(CH3O)Si(CH2)3Cl,[(C 14 H 29 O-(CH2-CH2O)6]2(CH3O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)2](CH3CH2O)2Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)3](CH3CH2O)2Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)4](CH3CH2O)2Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)5](CH3CH2O)2Si(CH2)3Cl [(C9H19 O-(CH2-CH2O)6](CH3CH2O)2Si(CH2)3Cl、[(C 12 H 25 O-(CH2-CH2O)2](CH3CH2O)2Si(CH2)3Cl、[(C 12 H 25 O-(CH2-CH2O)3](CH3CH2O)2Si(CH2)3Cl、[(C 12 H 25 O-(CH2-CH2O)4](CH3CH2O)2Si(CH2)3Cl、[(C 12 H 25 O-(CH2-CH2O)5](CH3CH2O)2Si(CH2)3Cl、[(C 12 H 25 O-(CH2-CH2O)6](CH3CH2O)2Si(CH2)3Cl、[(C 13 H 27 O-(CH2-CH2O)2](CH3CH2O)2Si(CH2)3Cl、[(C 13 H 27 O-(CH2-CH2O)3](CH3CH2O)2Si(CH2)3Cl、[(C 13 H 27 O-(CH2-CH2O)4](CH3CH2O)2Si(CH2)3Cl、[(C 13 H 27 O-(CH2-CH2O)5](CH3CH2O)2Si(CH2)3Cl、[(C 13 H 27 O-(CH2-CH2O)6](CH3CH2O)2Si(CH2)3Cl、[(C 14 H 29 O-(CH2-CH2O)2](CH3CH2O)2Si(CH2)3Cl、[(C 14 H 29 O-(CH2-CH2O)3](CH3CH2O)2Si(CH2)3Cl、[(C 14 H 29 O-(CH2-CH2O)4](CH3CH2O)2Si(CH2)3Cl、[(C 14 H 29 O-(CH2-CH2O)5](CH3CH2O)2Si(CH2)3Cl、[(C 14 H 29O-(CH2-CH2O)6](CH3CH2O)2Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)2]2(CH3CH2O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)3]2(CH3CH2O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)4]2(CH3CH2O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)5]2(CH3CH2O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)6]2(CH3CH2O)Si(CH2)3Cl,[(C 12 H 25 O-(CH2-CH2O)2]2(CH3CH2O)Si(CH2)3Cl,[(C 12 H 25 O-(CH2-CH2O)3]2(CH3CH2O)Si(CH2)3Cl,[(C 12 H 25 O-(CH2-CH2O)4]2(CH3CH2O)Si(CH2)3Cl,[(C 12 H 25 O-(CH2-CH2O)5]2(CH3CH2O)Si(CH2)3Cl,[(C 12 H 25 O-(CH2-CH2O)6]2(CH3CH2O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)2]2(CH3CH2O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)3]2(CH3CH2O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)4]2(CH3CH2O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)5]2(CH3CH2O)Si(CH2)3Cl,[(C 13 H 27 O-(CH2-CH2O)6]2(CH3CH2O)Si(CH2)3Cl,[(C 14 H 29O-(CH2-CH2O)2]2(CH3CH2O)Si(CH2)3Cl,[(C 14 H 29 O-(CH2-CH2O)3]2(CH3CH2O)Si(CH2)3Cl,[(C 14 H 29 O-(CH2-CH2O)4]2(CH3CH2O)Si(CH2)3Cl,[(C 14 H 29 O-(CH2-CH2O)5]2(CH3CH2O)Si(CH2)3Cl,[(C 14 H 29 O-(CH2-CH2O)6]2(CH3CH2O)Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)2]3Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)3]3Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)4]3Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)5]3Si(CH2)3Cl [(C9H 19 O-(CH2-CH2O)6]3Si(CH2)3Cl [(C 12 H 25 O-(CH2-CH2O)2]3Si(CH2)3Cl [(C 12 H 25 O-(CH2-CH2O)3]3Si(CH2)3Cl [(C 12 H 25 O-(CH2-CH2O)4]3Si(CH2)3Cl [(C 12 H 25 O-(CH2-CH2O)5]3Si(CH2)3Cl [(C 12 H 25 O-(CH2-CH2O)6]3Si(CH2)3Cl [(C 13 H 27 O-(CH2-CH2O)2]3Si(CH2)3Cl [(C 13 H 27 O-(CH2-CH2O)3]3Si(CH2)3Cl [(C 13 H 27 O-(CH2-CH2O)4]3Si(CH2)3Cl [(C 13 H 27O-(CH2-CH2O)5]3Si(CH2)3Cl, [(C 13 H 27 O-(CH2-CH2O)6]3Si(CH2)3Cl, [(C 14 H 29 O-(CH2-CH2O)2]3Si(CH2)3Cl, [(C 14 H 29 O-(CH2-CH2O)3]3Si(CH2)3Cl, [(C 14 H 29 O-(CH2-CH2O)4]3Si(CH2)3Cl, [(C 14 H 29 O-(CH2-CH2O)5]3Si(CH2)3Cl or [(C 14 H 29 O-(CH2-CH2O)6]3Si(CH2)3Cl.

[0032] The phase transfer catalyst of formula III can be: [N(CH3)4]X, [N(C2H5)4]X, [N(C3H7)4]X, [N(C4H9)4]X, [N(C5H 11 )4]X, [N(C6H 13 )4]X, [N(C7H 15 )4]X, [N(C8H 17 )4]X, [N(C9H 19 )4]X、[N(C 10 H 21 )4]X, [N(C2H5)(CH3)3]X, [N(C2H5)2(CH3)2]X, [N(C2H5)3(CH3)]X, [N(C3H7)(CH3)3]X, [N(C3H7)2 (CH3)2]X, [N(C3H7)3(CH3)]X, [N(C4H9)(CH3)3]X, [N(C4H9)2(CH3)2]X, [N(C4H9)3(CH3)]X, [N(C5H 11 )(CH3)3]X, [N(C5H 11 )2(CH3)2]X, [N(C5H 11 )3(CH3)]X, [N(C6H 13 )(CH3)3]X, [N(C6H 13 )2(CH3)2]X, [N(C6H 13 )3(CH3)]X, [N(C7H 15 )(CH3)3]X, [N(C7H 15)2(CH3)2]X、[N(C7H 15 )3(CH3)]X、[N(C8H 17 )(CH3)3]X、[N(C8H 17 )2(CH3)2]X、[N(C8H 17 )3(CH3)]X、[N(C9H 19 )(CH3)3]X、[N(C9H 19 )2(CH3)2]X、[N(C9H 19 )3(CH3)]X、[N(C 10 H 21 )(CH3)3]X、[N(C 10 H 21 )2(CH3)2]X、[N(C 10 H 21 )3(CH3)]X、[N(C3H7)(C2H5)3]X、[N(C3H7)2(C2H5)2]X、[N(C3H7)3(C2H5)]X、[N(C4H9)(C2H5)3]X、[N(C4H9)2(C2H5)2]X、[N(C4H9)3(C2H5)]X、[N(C5H 11 )(C2H5)3]X、[N(C5H 11 )2(C2H5)2]X、[N(C5H 11 )3(C2H5)]X、[N(C6H 13 )(C2H5)3]X、[N(C6H 13 )2(C2H5)2]X、[N(C6H 13 )3(C2H5)]X、[N(C7H 15 )(C2H5)3]X、[N(C7H 15 )2(C2H5)2]X、[N(C7H 15 )3(C2H5)]X、[N(C8H 17 )(C2H5)3]X、[N(C8H 17 )2(C2H5)2]X、[N(C8H 17 )3(C2H5)]X、[N(C9H 19 )(C2H5)3]X、[N(C9H 19 )2(C2H5)2]X、[N(C9H 19 )3(C2H5)]X、[N(C 10 H 21 )(C2H5)3]X、[N(C 10 H 21 )2(C2H5)2]X、[N(C10 H 21 )3(C2H5)]X、[N(C4H9)(C3H7)3]X、[N(C4H9)2(C3H7)2]X、[N(C4H9)3(C3H7)]X、[N(C5H 11 )(C3H7)3]X、[N(C5H 11 )2(C3H7)2]X、[N(C5H 11 )3(C3H7)]X、[N(C6H 13 )(C3H7)3]X、[N(C6H 13 )2(C3H7)2]X、[N(C6H 13 )3(C3H7)]X、[N(C7H 15 )(C3H7)3]X、[N(C7H 15 )2(C3H7)2]X、[N(C7H 15 )3(C3H7)]X、[N(C8H 17 )(C3H7)3]X、[N(C8H 17 )2(C3H7)2]X、[N(C8H 17 )3(C3H7)]X、[N(C9H 19 )(C3H7)3]X、[N(C9H 19 )2(C3H7)2]X、[N(C9H 19 )3(C3H7)]X、[N(C 10 H 21 )(C3H7)3]X、[N(C 10 H 21 )2(C3H7)2]X、[N(C 10 H 21 )3(C3H7)]X、[N(C5H 11 )(C4H9)3]X、[N(C5H 11 )2(C4H9)2]X、[N(C5H 11 )3(C4H9)]X、[N(C6H 13 )(C4H9)3]X、[N(C6H 13 )2(C4H9)2]X、[N(C6H 13 )3(C4H9)]X、[N(C7H 15 )(C4H9)3]X、[N(C7H 15 )2(C4H9)2]X、[N(C7H 15 )3(C4H9)]X、[N(C8H 17 )(C4H9)3]X、[N(C8H 17)2(C4H9)2]X、[N(C8H 17 )3(C4H9)]X、[N(C9H 19 )(C4H9)3]X、[N(C9H 19 )2(C4H9)2]X、[N(C9H 19 )3(C4H9)]X、[N(C 10 H 21 )(C4H9)3]X、[N(C 10 H 21 )2(C4H9)2]X、[N(C 10 H 21 )3(C4H9)]X、[N(C6H 13 )(C5H 11 )3]X、[N(C6H 13 )2(C5H 11 )2]X、[N(C6H 13 )3(C5H 11 )]X、[N(C7H 15 )(C5H 11 )3]X、[N(C7H 15 )2(C5H 11 )2]X、[N(C7H 15 )3(C5H 11 )]X、[N(C8H 17 )(C5H 11 )3]X、[N(C8H 17 )2(C5H 11 )2]X、[N(C8H 17 )3(C5H 11 )]X、[N(C9H 19 )(C5H 11 )3]X、[N(C9H 19 )2(C5H 11 )2]X、[N(C9H 19 )3(C5H 11 )]X、[N(C 10 H 21 )(C5H 11 )3]X、[N(C 10 H 21 )2(C5H 11 )2]X、[N(C 10 H 21 )3(C5H 11 )]X、[N(C7H 15 )(C6H 13 )3]X、[N(C7H 15 )2(C6H13 )2]X、[N(C7H 15 )3(C6H 13 )]X、[N(C8H 17 )(C6H 13 )3]X、[N(C8H 17 )2(C6H 13 )2]X、[N(C8H 17 )3(C6H 13 )]X、[N(C9H 19 )(C6H 13 )3]X、[N(C9H 19 )2(C6H 13 )2]X、[N(C9H 19 )3(C6H 13 )]X、[N(C 10 H 21 )(C6H 13 )3]X、[N(C 10 H 21 )2(C6H 13 )2]X、[N(C 10 H 21 )3(C6H 13 )]X、[N(C8H 17 )(C7H 15 )3]X、[N(C8H 17 )2(C7H 15 )2]X、[N(C8H 17 )3(C7H 15 )]X、[N(C9H 19 )(C7H 15 )3]X、[N(C9H 19 )2(C7H 15 )2]X、[N(C9H 19 )3(C7H 15 )]X、[N(C 10 H 21 )(C7H 15 )3]X、[N(C 10 H 21 )2(C7H 15 )2]X、[N(C 10 H 21 )3(C7H 15 )]X、[N(C9H 19 )(C8H 17 )3]X、[N(C9H 19 )2(C8H 17 )2]X、[N(C9H 19)3(C8H 17 )]X、[N(C 10 H 21 )(C8H 17 )3]X、[N(C 10 H 21 )2(C8H 17 )2]X、[N(C 10 H 21 )3(C8H 17 )]X、[N(C 10 H 21 )(C9H 19 )3]X、[N(C 10 H 21 )2(C9H 19 )2]X、[N(C 10 H 21 )3(C9H 19 )]X、[N(CH3)(C 10 H 21 )(C2H5)2]X、[N(CH3)(C 10 H 21 )2(C2H5)]X、[N(CH3)(C 10 H 21 )(C3H7)2]X、[N(CH3)(C 10 H 21 )2(C3H7)]X、[N(CH3)(C 10 H 21 )(C4H9)2]X、[N(CH3)(C 10 H 21 )2(C4H9)]X、[N(CH3)(C 10 H 21 )(C5H 11 )2]X、[N(CH3)(C 10 H 21 )2(C5H 11 )]X、[N(CH3)(C 10 H 21 )(C6H 13 )2]X、[N(CH3)(C 10 H 21 )2(C6H 13 )]X、[N(CH3)(C 10 H 21 )(C7H 15 )2]X、[N(CH3)(C 10 H 21 )2(C7H 15 )]X、[N(CH3)(C10 H 21 )(C8H 17 )2]X、[N(CH3)(C 10 H 21 )2(C8H 17 )]X、[N(CH3)(C 10 H 21 )(C9H 19 )2]X、[N(CH3)(C 10 H 21 )2(C9H 19 )]X、[N(CH3)(C9H 19 )(C2H5)2]X、[N(CH3)(C9H 19 )2(C2H5)]X、[N(CH3)(C9H 19 )(C3H7)2]X、[N(CH3)(C9H 19 )2(C3H7)]X、[N(CH3)(C9H 19 )(C4H9)2]X、[N(CH3)(C9H 19 )2(C4H9)]X、[N(CH3)(C9H 19 )(C5H 11 )2]X、[N(CH3)(C9H 19 )2(C5H 11 )]X、[N(CH3)(C9H 19 )(C6H 13 )2]X、[N(CH3)(C9H 19 )2(C6H 13 )]X、[N(CH3)(C9H 19 )(C7H 15 )2]X、[N(CH3)(C9H 19 )2(C7H 15 )]X、[N(CH3)(C9H 19 )(C8H 17 )2]X、[N(CH3)(C9H 19 )2(C8H 17 )]X、[N(CH3)(C8H 17 )(C2H5)2]X、[N(CH3)(C8H 17 )2(C2H5)]X、[N(CH3)(C8H 17 )(C3H7)2]X、[N(CH3)(C8H 17 )2(C3H7)]X、[N(CH3)(C8H 17 )(C4H9)2]X、[N(CH3)(C8H17 )2(C4H9)]X、[N(CH3)(C8H 17 )(C5H 11 )2]X、[N(CH3)(C8H 17 )2(C5H 11 )]X、[N(CH3)(C8H 17 )(C6H 13 )2]X、[N(CH3)(C8H 17 )2(C6H 13 )]X、[N(CH3)(C8H 17 )(C7H 15 )2]X、[N(CH3)(C8H 17 )2(C7H 15 )]X、[N(CH3)(C7H 15 )(C2H5)2]X、[N(CH3)(C7H 15 )2(C2H5)]X、[N(CH3)(C7H 15 )(C3H7)2]X、[N(CH3)(C7H 15 )2(C3H7)]X、[N(CH3)(C7H 15 )(C4H9)2]X、[N(CH3)(C7H 15 )2(C4H9)]X、[N(CH3)(C7H 15 )(C5H 11 )2]X、[N(CH3)(C7H 15 )2(C5H 11 )]X、[N(CH3)(C7H 15 )(C6H 13 )2]X、[N(CH3)(C7H 15 )2(C6H 13 )]X、[N(CH3)(C6H 13 )(C2H5)2]X、[N(CH3)(C6H 13 )2(C2H5)]X、[N(CH3)(C6H 13 )(C3H7)2]X、[N(CH3)(C6H 13 )2(C3H7)]X、[N(CH3)(C6H 13 )(C4H9)2]X、[N(CH3)(C6H 13 )2(C4H9)]X、[N(CH3)(C6H 13 )(C5H 11 )2]X、[N(CH3)(C6H 13 )2(C5H 11)]X、[N(CH3)(C5H 11 )(C2H5)2]X、[N(CH3)(C5H 11 )2(C2H5)]X、[N(CH3)(C5H 11 )(C3H7)2]X、[N(CH3)(C5H 11 )2(C3H7)]X、[N(CH3)(C5H 11 )(C4H9)2]X、[N(CH3)(C5H 11 )2(C4H9)]X、[N(CH3)(C4H9)(C2H5)2]X、[N(CH3)(C4H9)2(C2H5)]X、[N(CH3)(C4H9)(C3H7)2]X、[N(CH3)(C4H9)2(C3H7)]X、[N(CH3)(C3H7)(C2H5)2]X、[N(CH3)(C3H7)2(C2H5)]X、[N(C2H5)(C 10 H 21 )(C3H7)2]X、[N(C2H5)(C 10 H 21 )2(C3H7)]X、[N(C2H5)(C 10 H 21 )(C4H9)2]X、[N(C2H5)(C 10 H 21 )2(C4H9)]X、[N(C2H5)(C 10 H 21 )(C5H 11 )2]X、[N(C2H5)(C 10 H 21 )2(C5H 11 )]X、[N(C2H5)(C 10 H 21 )(C6H 13 )2]X、[N(C2H5)(C 10 H 21 )2(C6H 13 )]X、[N(C2H5)(C 10 H 21 )(C7H 15 )2]X、[N(C2H5)(C 10 H 21 )2(C7H 15 )]X、[N(C2H5)(C 10 H 21 )(C8H 17 )2]X、[N(C2H5)(C 10 H 21)2(C8H 17 )]X、[N(C2H5)(C 10 H 21 )(C9H 19 )2]X、[N(C2H5)(C 10 H 21 )2(C9H 19 )]X、[N(C2H5)(C9H 19 )(C3H7)2]X、[N(C2H5)(C9H 19 )2(C3H7)]X、[N(C2H5)(C9H 19 )(C4H9)2]X、[N(C2H5)(C9H 19 )2(C4H9)]X、[N(C2H5)(C9H 19 )(C5H 11 )2]X、[N(C2H5)(C9H 19 )2(C5H 11 )]X、[N(C2H5)(C9H 19 )(C6H 13 )2]X、[N(C2H5)(C9H 19 )2(C6H 13 )]X、[N(C2H5)(C9H 19 )(C7H 15 )2]X、[N(C2H5)(C9H 19 )2(C7H 15 )]X、[N(C2H5)(C9H 19 )(C8H 17 )2]X、[N(C2H5)(C9H 19 )2(C8H 17 )]X、[N(C2H5)(C8H 17 )(C3H7)2]X、[N(C2H5)(C8H 17 )2(C3H7)]X、[N(C2H5)(C8H 17 )(C4H9)2]X、[N(C2H5)(C8H 17 )2(C4H9)]X、[N(C2H5)(C8H 17 )(C5H 11 )2]X、[N(C2H5)(C8H 17 )2(C5H 11 )]X、[N(C2H5)(C8H 17 )(C6H 13 )2]X、[N(C2H5)(C8H 17 )2(C6H 13)]X、[N(C2H5)(C8H 17 )(C7H 15 )2]X、[N(C2H5)(C8H 17 )2(C7H 15 )]X、[N(C2H5)(C7H 15 )(C3H7)2]X、[N(C2H5)(C7H 15 )2(C3H7)]X、[N(C2H5)(C7H 15 )(C4H9)2]X、[N(C2H5)(C7H 15 )2(C4H9)]X、[N(C2H5)(C7H 15 )(C5H 11 )2]X、[N(C2H5)(C7H 15 )2(C5H 11 )]X、[N(C2H5)(C7H 15 )(C6H 13 )2]X、[N(C2H5)(C7H 15 )2(C6H 13 )]X、[N(C2H5)(C6H 13 )(C3H7)2]X、[N(C2H5)(C6H 13 )2(C3H7)]X、[N(C2H5)(C6H 13 )(C4H9)2]X、[N(C2H5)(C6H 13 )2(C4H9)]X、[N(C2H5)(C6H 13 )(C5H 11 )2]X、[N(C2H5)(C6H 13 )2(C5H 11 )]X、[N(C2H5)(C5H 11 )(C3H7)2]X、[N(C2H5)(C5H 11 )2(C3H7)]X、[N(C2H5)(C5H 11 )(C4H9)2]X、[N(C2H5)(C5H 11 )2(C4H9)]X、[N(C2H5)(C4H9)(C3H7)2]X、[N(C2H5)(C4H9)2(C3H7)]X、[N(C3H7)(C 10 H 21 )(C4H9)2]X、[N(C3H7)(C 10 H 21 )2(C4H9)]X、[N(C3H7)(C 10 H 21)(C5H 11 )2]X、[N(C3H7)(C 10 H 21 )2(C5H 11 )]X、[N(C3H7)(C 10 H 21 )(C6H 13 )2]X、[N(C3H7)(C 10 H 21 )2(C6H 13 )]X、[N(C3H7)(C 10 H 21 )(C7H 15 )2]X、[N(C3H7)(C 10 H 21 )2(C7H 15 )]X、[N(C3H7)(C 10 H 21 )(C8H 17 )2]X、[N(C3H7)(C 10 H 21 )2(C8H 17 )]X、[N(C3H7)(C 10 H 21 )(C9H 19 )2]X、[N(C3H7)(C 10 H 21 )2(C9H 19 )]X、[N(C3H7)(C9H 19 )(C4H9)2]X、[N(C3H7)(C9H 19 )2(C4H9)]X、[N(C3H7)(C9H 19 )(C5H 11 )2]X、[N(C3H7)(C9H 19 )2(C5H 11 )]X、[N(C3H7)(C9H 19 )(C6H 13 )2]X、[N(C3H7)(C9H 19 )2(C6H 13 )]X、[N(C3H7)(C9H 19 )(C7H 15 )2]X、[N(C3H7)(C9H 19 )2(C7H 15 )]X、[N(C3H7)(C9H 19 )(C8H 17 )2]X、[N(C3H7)(C9H 19<h2 style=";text-align:left;direction:ltr">)2(C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> )]X、[N(C3H7)(C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> (C4H9)2]X、[N(C3H7)(C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> )2(C4H9)]X、[N(C3H7)(C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> (C5H)<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> )2]X、[N(C3H7)(C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> )2(C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> )]X、[N(C3H7)(C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> (C6H)<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> )2]X、[N(C3H7)(C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> )2(C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> )]X、[N(C3H7)(C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> (C7H)<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> )2]X、[N(C3H7)(C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> )2(C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> )]X、[N(C3H7)(C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> (C4H9)2]X、[N(C3H7)(C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> )2(C4H9)]X、[N(C3H7)(C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> (C5H)<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> )2]X、[N(C3H7)(C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> )2(C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> )]X、[N(C3H7)(C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> (C6H)<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> )2]X、[N(C3H7)(C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> )2(C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> )]X、[N(C3H7)(C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> (C4H9)2]X、[N(C3H7)(C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> )2(C4H9)]X、[N(C3H7)(C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> (C5H)<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> )2]X、[N(C3H7)(C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> )2(C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> )]X、[N(C3H7)(C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> (C4H9)2]X、[N(C3H7)(C5H)<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> )2(C4H9)]X、[N(C4H9)(C<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 21 <h2 style=";text-align:left;direction:ltr"> (C5H)<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> )2]X、[N(C4H9)(C<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 21 <h2 style=";text-align:left;direction:ltr"> )2(C5H<h2 style=";text-align:left;direction:ltr"> 11)]X、[N(C4H9)(C 10 H 21 )(C6H 13 )2]X、[N(C4H9)(C 10 H 21 )2(C6H 13 )]X、[N(C4H9)(C 10 H 21 )(C7H 15 )2]X、[N(C4H9)(C 10 H 21 )2(C7H 15 )]X、[N(C4H9)(C 10 H 21 )(C8H 17 )2]X、[N(C4H9)(C 10 H 21 )2(C8H 17 )]X、[N(C4H9)(C 10 H 21 )(C9H 19 )2]X、[N(C4H9)(C 10 H 21 )2(C9H 19 )]X、[N(C4H9)(C9H 19 )(C5H 11 )2]X、[N(C4H9)(C9H 19 )2(C5H 11 )]X、[N(C4H9)(C9H 19 )(C6H 13 )2]X、[N(C4H9)(C9H 19 )2(C6H 13 )]X、[N(C4H9)(C9H 19 )(C7H 15 )2]X、[N(C4H9)(C9H 19 )2(C7H 15 )]X、[N(C4H9)(C9H 19 )(C8H 17 )2]X、[N(C4H9)(C9H 19 )2(C8H 17 )]X、[N(C4H9)(C8H 17 )(C5H 11 )2]X、[N(C4H9)(C8H 17 )2(C5H 11 )]X、[N(C4H9)(C8H 17 )(C6H13 )2]X、[N(C4H9)(C8H 17 )2(C6H 13 )]X、[N(C4H9)(C8H 17 )(C7H 15 )2]X、[N(C4H9)(C8H 17 )2(C7H 15 )]X、[N(C4H9)(C7H 15 )(C5H 11 )2]X、[N(C4H9)(C7H 15 )2(C5H 11 )]X、[N(C4H9)(C7H 15 )(C6H 13 )2]X、[N(C4H9)(C7H 15 )2(C6H 13 )]X、[N(C4H9)(C6H 13 )(C5H 11 )2]X、[N(C4H9)(C6H 13 )2(C5H 11 )]X、[N(C5H 11 )(C 10 H 21 )(C6H 13 )2]X、[N(C5H 11 )(C 10 H 21 )2(C6H 13 )]X、[N(C5H 11 )(C 10 H 21 )(C7H 15 )2]X、[N(C5H 11 )(C 10 H 21 )2(C7H 15 )]X、[N(C5H 11 )(C 10 H 21 )(C8H 17 )2]X、[N(C5H 11 )(C 10 H 21 )2(C8H 17 )]X、[N(C5H 11 )(C 10 H 21 )(C9H 19 )2]X、[N(C5H 11 )(C 10 H 21)2(C9H 19 )]X、[N(C5H 11 )(C9H 19 )(C6H 13 )2]X、[N(C5H 11 )(C9H 19 )2(C6H 13 )]X、[N(C5H 11 )(C9H 19 )(C7H 15 )2]X、[N(C5H 11 )(C9H 19 )2(C7H 15 )]X、[N(C5H 11 )(C9H 19 )(C8H 17 )2]X、[N(C5H 11 )(C9H 19 )2(C8H 17 )]X、[N(C5H 11 )(C8H 17 )(C6H 13 )2]X、[N(C5H 11 )(C8H 17 )2(C6H 13 )]X、[N(C5H 11 )(C8H 17 )(C7H 15 )2]X、[N(C5H 11 )(C8H 17 )2(C7H 15 )]X、[N(C5H 11 )(C7H 15 )(C6H 13 )2]X、[N(C5H 11 )(C7H 15 )2(C6H 13 )]X、[N(C6H 13 )(C 10 H 21 )(C7H 15 )2]X、[N(C6H 13 )(C 10 H 21 )2(C7H 15 )]X、[N(C6H 13 )(C 10 H 21 )(C8H 17 )2]X、[N(C6H 13 )(C 10 H21 )2(C8H 17 )]X、[N(C6H 13 )(C 10 H 21 )(C9H 19 )2]X、[N(C6H 13 )(C 10 H 21 )2(C9H 19 )]X、[N(C6H 13 )(C9H 19 )(C7H 15 )2]X、[N(C6H 13 )(C9H 19 )2(C7H 15 )]X、[N(C6H 13 )(C9H 19 )(C8H 17 )2]X、[N(C6H 13 )(C9H 19 )2(C8H 17 )]X、[N(C6H 13 )(C8H 17 )(C7H 15 )2]X、[N(C6H 13 )(C8H 17 )2(C7H 15 )]X、[N(C7H 15 )(C 10 H 21 )(C8H 17 )2]X、[N(C7H 15 )(C 10 H 21 )2(C8H 17 )]X、[N(C7H 15 )(C 10 H 21 )(C9H 19 )2]X、[N(C7H 15 )(C 10 H 21 )2(C9H 19 )]X、[N(C7H 15 )(C9H 19 )(C8H 17 )2]X、[N(C7H 15 )(C9H 19 )2(C8H 17 )]X、[N(C8H 17 )(C 10 H 21 )(C9H19 )2]X、[N(C8H 17 )(C 10 H 21 )2(C9H 19 )]X、[P(CH3)4]X、[P(C2H5)4]X、[P(C3H7)4]X、[P(C4H9)4]X、[P(C5H 11 )4]X、[P(C6H 13 )4]X、[P(C7H 15 )4]X、[P(C8H 17 )4]X、[P(C9H 19 )4]X、[P(C 10 H 21 )4]X、[P(C2H5)(CH3)3]X、[P(C2H5)2(CH3)2]X、[P(C2H5)3(CH3)]X、[P(C3H7)(CH3)3]X、[P(C3H7)2(CH3)2]X、[P(C3H7)3(CH3)]X、[P(C4H9)(CH3)3]X、[P(C4H9)2(CH3)2]X、[P(C4H9)3(CH3)]X、[P(C5H 11 )(CH3)3]X、[P(C5H 11 )2(CH3)2]X、[P(C5H 11 )3(CH3)]X、[P(C6H 13 )(CH3)3]X、[P(C6H 13 )2(CH3)2]X、[P(C6H 13 )3(CH3)]X、[P(C7H 15 )(CH3)3]X、[P(C7H 15 )2(CH3)2]X、[P(C7H 15 )3(CH3)]X、[P(C8H 17 )(CH3)3]X、[P(C8H 17 )2(CH3)2]X、[P(C8H 17 )3(CH3)]X、[P(C9H 19 )(CH3)3]X、[P(C9H 19 )2(CH3)2]X、[P(C9H 19 )3(CH3)]X、[P(C 10 H 21 )(CH3)3]X、[P(C 10 H 21 )2(CH3)2]X、[P(C 10 H 21)3(CH3)]X、[P(C3H7)(C2H5)3]X、[P(C3H7)2(C2H5)2]X、[P(C3H7)3(C2H5)]X、[P(C4H9)(C2H5)3]X、[P(C4H9)2(C2H5)2]X、[P(C4H9)3(C2H5)]X、[P(C5H 11 )(C2H5)3]X、[P(C5H 11 )2(C2H5)2]X、[P(C5H 11 )3(C2H5)]X、[P(C6H 13 )(C2H5)3]X、[P(C6H 13 )2(C2H5)2]X、[P(C6H 13 )3(C2H5)]X、[P(C7H 15 )(C2H5)3]X、[P(C7H 15 )2(C2H5)2]X、[P(C7H 15 )3(C2H5)]X、[P(C8H 17 )(C2H5)3]X、[P(C8H 17 )2(C2H5)2]X、[P(C8H 17 )3(C2H5)]X、[P(C9H 19 )(C2H5)3]X、[P(C9H 19 )2(C2H5)2]X、[P(C9H 19 )3(C2H5)]X、[P(C 10 H 21 )(C2H5)3]X、[P(C 10 H 21 )2(C2H5)2]X、[P(C 10 H 21 )3(C2H5)]X、[P(C4H9)(C3H7)3]X、[P(C4H9)2(C3H7)2]X、[P(C4H9)3(C3H7)]X、[P(C5H 11 )(C3H7)3]X、[P(C5H 11 )2(C3H7)2]X、[P(C5H 11 )3(C3H7)]X、[P(C6H 13 )(C3H7)3]X、[P(C6H 13 )2(C3H7)2]X、[P(C6H 13 )3(C3H7)]X、[P(C7H 15 )(C3H7)3]X、[P(C7H 15)2(C3H7)2]X、[P(C7H 15 )3(C3H7)]X、[P(C8H 17 )(C3H7)3]X、[P(C8H 17 )2(C3H7)2]X、[P(C8H 17 )3(C3H7)]X、[P(C9H 19 )(C3H7)3]X、[P(C9H 19 )2(C3H7)2]X、[P(C9H 19 )3(C3H7)]X、[P(C 10 H 21 )(C3H7)3]X、[P(C 10 H 21 )2(C3H7)2]X、[P(C 10 H 21 )3(C3H7)]X、[P(C5H 11 )(C4H9)3]X、[P(C5H 11 )2(C4H9)2]X、[P(C5H 11 )3(C4H9)]X、[P(C6H 13 )(C4H9)3]X、[P(C6H 13 )2(C4H9)2]X、[P(C6H 13 )3(C4H9)]X、[P(C7H 15 )(C4H9)3]X、[P(C7H 15 )2(C4H9)2]X、[P(C7H 15 )3(C4H9)]X、[P(C8H 17 )(C4H9)3]X、[P(C8H 17 )2(C4H9)2]X、[P(C8H 17 )3(C4H9)]X、[P(C9H 19 )(C4H9)3]X、[P(C9H 19 )2(C4H9)2]X、[P(C9H 19 )3(C4H9)]X、[P(C 10 H 21 )(C4H9)3]X、[P(C 10 H 21 )2(C4H9)2]X、[P(C 10 H 21 )3(C4H9)]X、[P(C6H 13 )(C5H 11 )3]X、[P(C6H 13 )2(C5H11 )2]X、[P(C6H 13 )3(C5H 11 )]X、[P(C7H 15 )(C5H 11 )3]X、[P(C7H 15 )2(C5H 11 )2]X、[P(C7H 15 )3(C5H 11 )]X、[P(C8H 17 )(C5H 11 )3]X、[P(C8H 17 )2(C5H 11 )2]X、[P(C8H 17 )3(C5H 11 )]X、[P(C9H 19 )(C5H 11 )3]X、[P(C9H 19 )2(C5H 11 )2]X、[P(C9H 19 )3(C5H 11 )]X、[P(C 10 H 21 )(C5H 11 )3]X、[P(C 10 H 21 )2(C5H 11 )2]X、[P(C 10 H 21 )3(C5H 11 )]X、[P(C7H 15 )(C6H 13 )3]X、[P(C7H 15 )2(C6H 13 )2]X、[P(C7H 15 )3(C6H 13 )]X、[P(C8H 17 )(C6H 13 )3]X、[P(C8H 17 )2(C6H 13 )2]X、[P(C8H 17 )3(C6H 13 )]X、[P(C9H 19 )(C6H 13 )3]X、[P(C9H 19 )2(C6H 13 )2]X、[P(C9H 19 )3(C6H 13 )]X、[P(C 10 H21 )(C6H 13 )3]X、[P(C 10 H 21 )2(C6H 13 )2]X、[P(C 10 H 21 )3(C6H 13 )]X、[P(C8H 17 )(C7H 15 )3]X、[P(C8H 17 )2(C7H 15 )2]X、[P(C8H 17 )3(C7H 15 )]X、[P(C9H 19 )(C7H 15 )3]X、[P(C9H 19 )2(C7H 15 )2]X、[P(C9H 19 )3(C7H 15 )]X、[P(C 10 H 21 )(C7H 15 )3]X、[P(C 10 H 21 )2(C7H 15 )2]X、[P(C 10 H 21 )3(C7H 15 )]X、[P(C9H 19 )(C8H 17 )3]X、[P(C9H 19 )2(C8H 17 )2]X、[P(C9H 19 )3(C8H 17 )]X、[P(C 10 H 21 )(C8H 17 )3]X、[P(C 10 H 21 )2(C8H 17 )2]X、[P(C 10 H 21 )3(C8H 17 )]X、[P(C 10 H 21 )(C9H 19 )3]X、[P(C 10 H 21 )2(C9H 19 )2]X、[P(C 10 H 21 )3(C9H19 )]X、[P(CH3)(C 10 H 21 )(C2H5)2]X、[P(CH3)(C 10 H 21 )2(C2H5)]X、[P(CH3)(C 10 H 21 )(C3H7)2]X、[P(CH3)(C 10 H 21 )2(C3H7)]X、[P(CH3)(C 10 H 21 )(C4H9)2]X、[P(CH3)(C 10 H 21 )2(C4H9)]X、[P(CH3)(C 10 H 21 )(C5H 11 )2]X、[P(CH3)(C 10 H 21 )2(C5H 11 )]X、[P(CH3)(C 10 H 21 )(C6H 13 )2]X、[P(CH3)(C 10 H 21 )2(C6H 13 )]X、[P(CH3)(C 10 H 21 )(C7H 15 )2]X、[P(CH3)(C 10 H 21 )2(C7H 15 )]X、[P(CH3)(C 10 H 21 )(C8H 17 )2]X、[P(CH3)(C 10 H 21 )2(C8H 17 )]X、[P(CH3)(C 10 H 21 )(C9H 19 )2]X、[P(CH3)(C 10 H 21 )2(C9H 19 )]X、[P(CH3)(C9H 19 )(C2H5)2]X、[P(CH3)(C9H 19 )2(C2H5)]X、[P(CH3)(C9H 19)(C3H7)2]X、[P(CH3)(C9H 19 )2(C3H7)]X、[P(CH3)(C9H 19 )(C4H9)2]X、[P(CH3)(C9H 19 )2(C4H9)]X、[P(CH3)(C9H 19 )(C5H 11 )2]X、[P(CH3)(C9H 19 )2(C5H 11 )]X、[P(CH3)(C9H 19 )(C6H 13 )2]X、[P(CH3)(C9H 19 )2(C6H 13 )]X、[P(CH3)(C9H 19 )(C7H 15 )2]X、[P(CH3)(C9H 19 )2(C7H 15 )]X、[P(CH3)(C9H 19 )(C8H 17 )2]X、[P(CH3)(C9H 19 )2(C8H 17 )]X、[P(CH3)(C8H 17 )(C2H5)2]X、[P(CH3)(C8H 17 )2(C2H5)]X、[P(CH3)(C8H 17 )(C3H7)2]X、[P(CH3)(C8H 17 )2(C3H7)]X、[P(CH3)(C8H 17 )(C4H9)2]X、[P(CH3)(C8H 17 )2(C4H9)]X、[P(CH3)(C8H 17 )(C5H 11 )2]X、[P(CH3)(C8H 17 )2(C5H 11 )]X、[P(CH3)(C8H 17 )(C6H 13 )2]X、[P(CH3)(C8H 17 )2(C6H 13 )]X、[P(CH3)(C8H 17 )(C7H 15 )2]X、[P(CH3)(C8H 17 )2(C7H 15 )]X、[P(CH3)(C7H15 )(C2H5)2]X、[P(CH3)(C7H 15 )2(C2H5)]X、[P(CH3)(C7H 15 )(C3H7)2]X、[P(CH3)(C7H 15 )2(C3H7)]X、[P(CH3)(C7H 15 )(C4H9)2]X、[P(CH3)(C7H 15 )2(C4H9)]X、[P(CH3)(C7H 15 )(C5H 11 )2]X、[P(CH3)(C7H 15 )2(C5H 11 )]X、[P(CH3)(C7H 15 )(C6H 13 )2]X、[P(CH3)(C7H 15 )2(C6H 13 )]X、[P(CH3)(C6H 13 )(C2H5)2]X、[P(CH3)(C6H 13 )2(C2H5)]X、[P(CH3)(C6H 13 )(C3H7)2]X、[P(CH3)(C6H 13 )2(C3H7)]X、[P(CH3)(C6H 13 )(C4H9)2]X、[P(CH3)(C6H 13 )2(C4H9)]X、[P(CH3)(C6H 13 )(C5H 11 )2]X、[P(CH3)(C6H 13 )2(C5H 11 )]X、[P(CH3)(C5H 11 )(C2H5)2]X、[P(CH3)(C5H 11 )2(C2H5)]X、[P(CH3)(C5H 11 )(C3H7)2]X、[P(CH3)(C5H 11 )2(C3H7)]X、[P(CH3)(C5H 11 )(C4H9)2]X、[P(CH3)(C5H 11)2(C4H9)]X、[P(CH3)(C4H9)(C2H5)2]X、[P(CH3)(C4H9)2(C2H5)]X、[P(CH3)(C4H9)(C3H7)2]X、[P(CH3)(C4H9)2(C3H7)]X、[P(CH3)(C3H7)(C2H5)2]X、[P(CH3)(C3H7)2(C2H5)]X、[P(C2H5)(C 10 H 21 )(C3H7)2]X、[P(C2H5)(C 10 H 21 )2(C3H7)]X、[P(C2H5)(C 10 H 21 )(C4H9)2]X、[P(C2H5)(C 10 H 21 )2(C4H9)]X、[P(C2H5)(C 10 H 21 )(C5H 11 )2]X、[P(C2H5)(C 10 H 21 )2(C5H 11 )]X、[P(C2H5)(C 10 H 21 )(C6H 13 )2]X、[P(C2H5)(C 10 H 21 )2(C6H 13 )]X、[P(C2H5)(C 10 H 21 )(C7H 15 )2]X、[P(C2H5)(C 10 H 21 )2(C7H 15 )]X、[P(C2H5)(C 10 H 21 )(C8H 17 )2]X、[P(C2H5)(C 10 H 21 )2(C8H 17 )]X、[P(C2H5)(C 10 H 21 )(C9H 19 )2]X、[P(C2H5)(C 10 H 21 )2(C9H 19 )]X、[P(C2H5)(C9H 19 )(C3H7)2]X、[P(C2H5)(C9H 19)2(C3H7)]X、[P(C2H5)(C9H 19 )(C4H9)2]X、[P(C2H5)(C9H 19 )2(C4H9)]X、[P(C2H5)(C9H 19 )(C5H 11 )2]X、[P(C2H5)(C9H 19 )2(C5H 11 )]X、[P(C2H5)(C9H 19 )(C6H 13 )2]X、[P(C2H5)(C9H 19 )2(C6H 13 )]X、[P(C2H5)(C9H 19 )(C7H 15 )2]X、[P(C2H5)(C9H 19 )2(C7H 15 )]X、[P(C2H5)(C9H 19 )(C8H 17 )2]X、[P(C2H5)(C9H 19 )2(C8H 17 )]X、[P(C2H5)(C8H 17 )(C3H7)2]X、[P(C2H5)(C8H 17 )2(C3H7)]X、[P(C2H5)(C8H 17 )(C4H9)2]X、[P(C2H5)(C8H 17 )2(C4H9)]X、[P(C2H5)(C8H 17 )(C5H 11 )2]X、[P(C2H5)(C8H 17 )2(C5H 11 )]X、[P(C2H5)(C8H 17 )(C6H 13 )2]X、[P(C2H5)(C8H 17 )2(C6H 13 )]X、[P(C2H5)(C8H 17 )(C7H 15 )2]X、[P(C2H5)(C8H 17 )2(C7H 15 )]X、[P(C2H5)(C7H 15 )(C3H7)2]X、[P(C2H5)(C7H 15 )2(C3H7)]X、[P(C2H5)(C7H 15)(C4H9)2]X、[P(C2H5)(C7H 15 )2(C4H9)]X、[P(C2H5)(C7H 15 )(C5H 11 )2]X、[P(C2H5)(C7H 15 )2(C5H 11 )]X、[P(C2H5)(C7H 15 )(C6H 13 )2]X、[P(C2H5)(C7H 15 )2(C6H 13 )]X、[P(C2H5)(C6H 13 )(C3H7)2]X、[P(C2H5)(C6H 13 )2(C3H7)]X、[P(C2H5)(C6H 13 )(C4H9)2]X、[P(C2H5)(C6H 13 )2(C4H9)]X、[P(C2H5)(C6H 13 )(C5H 11 )2]X、[P(C2H5)(C6H 13 )2(C5H 11 )]X、[P(C2H5)(C5H 11 )(C3H7)2]X、[P(C2H5)(C5H 11 )2(C3H7)]X、[P(C2H5)(C5H 11 )(C4H9)2]X、[P(C2H5)(C5H 11 )2(C4H9)]X、[P(C2H5)(C4H9)(C3H7)2]X、[P(C2H5)(C4H9)2(C3H7)]X、[P(C3H7)(C 10 H 21 )(C4H9)2]X、[P(C3H7)(C 10 H 21 )2(C4H9)]X、[P(C3H7)(C 10 H 21 )(C5H 11 )2]X、[P(C3H7)(C 10 H 21 )2(C5H 11 )]X、[P(C3H7)(C 10 H 21 )(C6H 13 )2]X、[P(C3H7)(C 10 H 21 )2(C6H 13)]X、[P(C3H7)(C 10 H 21 )(C7H 15 )2]X、[P(C3H7)(C 10 H 21 )2(C7H 15 )]X、[P(C3H7)(C 10 H 21 )(C8H 17 )2]X、[P(C3H7)(C 10 H 21 )2(C8H 17 )]X、[P(C3H7)(C 10 H 21 )(C9H 19 )2]X、[P(C3H7)(C 10 H 21 )2(C9H 19 )]X、[P(C3H7)(C9H 19 )(C4H9)2]X、[P(C3H7)(C9H 19 )2(C4H9)]X、[P(C3H7)(C9H 19 )(C5H 11 )2]X、[P(C3H7)(C9H 19 )2(C5H 11 )]X、[P(C3H7)(C9H 19 )(C6H 13 )2]X、[P(C3H7)(C9H 19 )2(C6H 13 )]X、[P(C3H7)(C9H 19 )(C7H 15 )2]X、[P(C3H7)(C9H 19 )2(C7H 15 )]X、[P(C3H7)(C9H 19 )(C8H 17 )2]X、[P(C3H7)(C9H 19 )2(C8H 17 )]X、[P(C3H7)(C8H 17 )(C4H9)2]X、[P(C3H7)(C8H 17 )2(C4H9)]X、[P(C3H7)(C8H 17 )(C5H 11 )2]X、[P(C3H7)(C8H 17 )2(C5H 11 )]X、[P(C3H7)(C8H17 )(C6H 13 )2]X、[P(C3H7)(C8H 17 )2(C6H 13 )]X、[P(C3H7)(C8H 17 )(C7H 15 )2]X、[P(C3H7)(C8H 17 )2(C7H 15 )]X、[P(C3H7)(C7H 15 )(C4H9)2]X、[P(C3H7)(C7H 15 )2(C4H9)]X、[P(C3H7)(C7H 15 )(C5H 11 )2]X、[P(C3H7)(C7H 15 )2(C5H 11 )]X、[P(C3H7)(C7H 15 )(C6H 13 )2]X、[P(C3H7)(C7H 15 )2(C6H 13 )]X、[P(C3H7)(C6H 13 )(C4H9)2]X、[P(C3H7)(C6H 13 )2(C4H9)]X、[P(C3H7)(C6H 13 )(C5H 11 )2]X、[P(C3H7)(C6H 13 )2(C5H 11 )]X、[P(C3H7)(C5H 11 )(C4H9)2]X、[P(C3H7)(C5H 11 )2(C4H9)]X、[P(C4H9)(C 10 H 21 )(C5H 11 )2]X、[P(C4H9)(C 10 H 21 )2(C5H 11 )]X、[P(C4H9)(C 10 H 21 )(C6H 13 )2]X、[P(C4H9)(C 10 H 21 )2(C6H 13 )]X、[P(C4H9)(C 10 H 21 )(C7H 15 )2]X、[P(C4H9)(C10 H 21 )2(C7H 15 )]X、[P(C4H9)(C 10 H 21 )(C8H 17 )2]X、[P(C4H9)(C 10 H 21 )2(C8H 17 )]X、[P(C4H9)(C 10 H 21 )(C9H 19 )2]X、[P(C4H9)(C 10 H 21 )2(C9H 19 )]X、[P(C4H9)(C9H 19 )(C5H 11 )2]X、[P(C4H9)(C9H 19 )2(C5H 11 )]X、[P(C4H9)(C9H 19 )(C6H 13 )2]X、[P(C4H9)(C9H 19 )2(C6H 13 )]X、[P(C4H9)(C9H 19 )(C7H 15 )2]X、[P(C4H9)(C9H 19 )2(C7H 15 )]X、[P(C4H9)(C9H 19 )(C8H 17 )2]X、[P(C4H9)(C9H 19 )2(C8H 17 )]X、[P(C4H9)(C8H 17 )(C5H 11 )2]X、[P(C4H9)(C8H 17 )2(C5H 11 )]X、[P(C4H9)(C8H 17 )(C6H 13 )2]X、[P(C4H9)(C8H 17 )2(C6H 13 )]X、[P(C4H9)(C8H 17 )(C7H 15 )2]X、[P(C4H9)(C8H 17 )2(C7H 15 )]X、[P(C4H9)(C7H 15 )(C5H 11)2]X、[P(C4H9)(C7H 15 )2(C5H 11 )]X、[P(C4H9)(C7H 15 )(C6H 13 )2]X、[P(C4H9)(C7H 15 )2(C6H 13 )]X、[P(C4H9)(C6H 13 )(C5H 11 )2]X、[P(C4H9)(C6H 13 )2(C5H 11 )]X、[P(C5H 11 )(C 10 H 21 )(C6H 13 )2]X、[P(C5H 11 )(C 10 H 21 )2(C6H 13 )]X、[P(C5H 11 )(C 10 H 21 )(C7H 15 )2]X、[P(C5H 11 )(C 10 H 21 )2(C7H 15 )]X、[P(C5H 11 )(C 10 H 21 )(C8H 17 )2]X、[P(C5H 11 )(C 10 H 21 )2(C8H 17 )]X、[P(C5H 11 )(C 10 H 21 )(C9H 19 )2]X、[P(C5H 11 )(C 10 H 21 )2(C9H 19 )]X、[P(C5H 11 )(C9H 19 )(C6H 13 )2]X、[P(C5H 11 )(C9H 19 )2(C6H 13 )]X、[P(C5H 11 )(C9H 19 )(C7H 15)2]X、[P(C5H 11 )(C9H 19 )2(C7H 15 )]X、[P(C5H 11 )(C9H 19 )(C8H 17 )2]X、[P(C5H 11 )(C9H 19 )2(C8H 17 )]X、[P(C5H 11 )(C8H 17 )(C6H 13 )2]X、[P(C5H 11 )(C8H 17 )2(C6H 13 )]X、[P(C5H 11 )(C8H 17 )(C7H 15 )2]X、[P(C5H 11 )(C8H 17 )2(C7H 15 )]X、[P(C5H 11 )(C7H 15 )(C6H 13 )2]X、[P(C5H 11 )(C7H 15 )2(C6H 13 )]X、[P(C6H 13 )(C 10 H 21 )(C7H 15 )2]X、[P(C6H 13 )(C 10 H 21 )2(C7H 15 )]X、[P(C6H 13 )(C 10 H 21 )(C8H 17 )2]X、[P(C6H 13 )(C 10 H 21 )2(C8H 17 )]X、[P(C6H 13 )(C 10 H 21 )(C9H 19 )2]X、[P(C6H 13 )(C 10 H 21 )2(C9H 19 )]X、[P(C6H 13 )(C9H19 )(C7H 15 )2]X, [P(C6H 13 )(C9H 19 )2(C7H 15 )]X, [P(C6H 13 )(C9H 19 )(C8H 17 )2]X, [P(C6H 13 )(C9H 19 )2(C8H 17 )]X, [P(C6H 13 )(C8H 17 )(C7H 15 )2]X, [P(C6H 13 )(C8H 17 )2(C7H 15 )]X、[P(C7H 15 )(C 10 H 21 )(C8H 17 )2]X, [P(C7H 15 )(C 10 H 21 )2(C8H 17 )]X、[P(C7H 15 )(C 10 H 21 )(C9H 19 )2]X, [P(C7H 15 )(C 10 H 21 )2(C9H 19 )]X、[P(C7H 15 )(C9H 19 )(C8H 17 )2]X, [P(C7H 15 )(C9H 19 )2(C8H 17 )]X, [P(C8H 17 )(C 10 H 21 )(C9H 19 )2]X, [P(C8H 17 )(C 10 H 21 )2(C9H 19 )]X.

[0033] The base used can be M 3-w CO3, M(OH) w 、M 3-w (HPO4), M(H2PO4) w、M3(PO4) w , wherein w is 1 or 2, and when w=1, M=Na or K, and when w=2, M=Ca or Mg. The base used may preferably be N a2 CO3 or NaOH.

[0034] The process according to the invention for preparing polysulfanesilanes of the formula I can be carried out at a temperature of 25°C to 200°C, preferably 70°C to 160°C.

[0035] In the process according to the invention for preparing polysulfanesilane of formula I, a phase transfer catalyst of formula III can be added and then a silane of formula II can be added to a silane of formula II in aqueous solution / suspension. y (preferably NaSH) and / or M z S (preferably Na2S) and / or M g S h , an aqueous phase prepared by alkali (preferably NaOH or Na2CO3) and sulfur.

[0036] In the process according to the invention for preparing polysulfanesilanes of formula I, M(SH) y and / or M z S and / or M g S h It can be prepared in situ from MOH and sulfur.

[0037] The molar ratio between the silane of the formula II used and the NaSH used can be between 0.35 and 1.0, preferably between 0.45 and 0.55.

[0038] The molar ratio between the silane of the formula II used and the base may be between 0.35 and 1.0, preferably between 0.45 and 0.60.

[0039] The molar ratio between the silane of the formula II used and the sulfur may be between 0.4 and 3.0, preferably between 0.5 and 1.5.

[0040] The molar ratio between the silane of the formula II and the phase transfer catalyst of the formula III used may be between 0.001 and 0.1, preferably between 0.003 and 0.05.

[0041] The process according to the invention for preparing polysulfanesilanes of the formula I can be carried out without organic solvents. The aqueous phase used can contain process salts from previous batches. During the preparation of the aqueous phase, a partial amount or the entire amount of the phase transfer catalyst of the formula III can be added. In the case of partial addition of the phase transfer catalyst of the formula III, the remaining amount can be added batchwise or continuously, preferably continuously, during the metered addition of the silane of the formula II. M(SH) for preparing polysulfanesilanes of the formula I y and / or Mz S and / or M g S h It can be prepared before or during the reaction.

[0042] In the reaction, the aqueous phase can be mixed with the silane of formula II. The aqueous phase can be metered into the silane of formula II or the silane of formula II can be metered into the aqueous phase. The silane of formula II is preferably metered into the aqueous phase. During the reaction, the silane of formula II can be added in batches or continuously, preferably continuously.

[0043] The method according to the invention can be carried out in a reaction vessel which is closed or open to the atmosphere. The contents of the reaction vessel can be mixed. A suitable method for mixing the contents of the reaction vessel is to circulate the contents of the reaction vessel externally or to stir the contents of the reaction vessel by means of a gas or a stirrer system, preferably a stirrer system. The process can be carried out continuously or intermittently.

[0044] Any portion of the remaining phase transfer catalyst of formula III may be added during the reaction batchwise or continuously, preferably continuously.

[0045] After reaction conversion, the aqueous phase can be separated from the organic phase.

[0046] The carrier steam used for carrier steam distillation can be generated in situ or externally, preferably externally. The carrier used for carrier steam distillation can be nitrogen, water vapor, alcohol or a combination of the above substances.

[0047] The carrier steam distillation may be a single-stage distillation, such as a still, or a multi-stage distillation, such as a plurality of stills or columns with trays or random packing, or a packed column, preferably a packed column.

[0048] The carrier steam distillation can be carried out continuously or batchwise, preferably continuously.

[0049] The support steam distillation can be carried out under reduced pressure, preferably at a pressure of less than 100 mbar absolute.

[0050] The reaction product can be separated from the aqueous phase by phase separation prior to carrier steam distillation. The reaction product can be separated by filtering solids such as NaCl prior to carrier steam distillation.

[0051] The reaction product may be purified by distillation prior to steam distillation of the support.

[0052] The top product from the steam distillation of the support can be further purified to recover the silicon-containing components.Degradation products of the phase transfer catalyst of formula III can be partially or completely removed from the silicon-containing components of the top product.

[0053] Removal of degradation products of the phase transfer catalyst of formula III from the top product of the steam distillation of the support may be carried out by treatment with ozone and / or distillation in either order.

[0054] If the degradation products of the phase transfer catalyst of the formula III are removed from the top product of the support steam distillation by carrying out a distillation, the distillation used may be a further support steam distillation.

[0055] The distillation for purifying the top product can be carried out as a separate distillation or as a component of a carrier steam distillation.

[0056] The distillative purification of the top product can be carried out before or after the condensation. The distillative purification of the top product can be carried out after the phase separation after the condensation.

[0057] The top product, from which degradation products of the phase transfer catalyst of the formula III have been partially or completely freed, can be used in any desired step outside the process or before the steam distillation of the support.

[0058] For the ozone treatment, pure ozone may be used, or ozone diluted in other gases, such as air, oxygen or nitrogen, preferably air.

[0059] The ozone treatment can be carried out continuously or intermittently, preferably continuously.

[0060] Ozone can be produced by an ozone generator.

[0061] The reaction product may be separated from the aqueous phase by phase separation prior to ozone treatment. The reaction product may be separated by filtering solids such as NaCl prior to ozone treatment.

[0062] The reaction product may be purified by distillation prior to ozone treatment.

[0063] Volatile degradation products from ozonation can be removed from the product by distillation.

[0064] For distillative removal of the volatile degradation products from the ozonation, continuous and batch distillation processes can be used. Thin-film evaporators can be used in particular for continuous distillation processes.

[0065] Degradation products formed in the PTC process, such as arsine, phosphine or amines, preferably tributylamine, can be separated or degraded from the phase transfer catalyst of the formula III by the process steps of steam distillation of the carrier and / or ozone treatment.

[0066] In addition, charcoal post-treatment can be performed. Activated carbon can be used for charcoal post-treatment. Charcoal post-treatment can be performed after carrier steam distillation and / or after ozone treatment.

[0067] The charcoal post-treatment can be carried out by adding charcoal to the polysulfanesilane of the formula I and subsequent filtering or by passing the polysulfanesilane of the formula I through a fixed bed containing charcoal.

[0068] Further post-treatment with iodine, chlorosilanes, peroxides or methyl iodide may be performed to remove degradation products of the phase transfer catalyst of formula III, such as tributylamine.

[0069] The present invention further provides the use of steam distillation and / or ozone treatment of the carrier for removing degradation products of the phase transfer catalyst.

[0070] The use of steam distillation and / or ozone treatment of the support for removing degradation products of the phase transfer catalyst, preferably of formula III, can be used to prepare sulfur-containing organosilanes, preferably polysulfanesilanes, thiocyanatosilanes and blocked and unblocked mercaptosilanes.

[0071] Activated carbon treatment may be performed downstream of the carrier steam distillation and / or ozone treatment.

[0072] The process according to the invention has the advantage that degradation products of the phase transfer catalyst of the formula III, some of which are toxic or harmful to health, are eliminated from the end product and that the storage stability (color and S distribution) is simultaneously improved.

[0073] Analytical gas chromatography (GC) of reaction mixtures and pure substances was performed using an Agilent 7820A gas chromatograph according to ASTM D 6843–02:

[0074] Analytical separation of sulfur-containing compounds and determination of sulfur chain length were performed according to ASTM D 6844–02 using an analytical HPLC Series 1260 Infinity II system from Agilent Technologies.

[0075] Column: Bakerbond C18 (RP), 5 μm, 4.6 x 250 mm, flow rate 1.50 ml / min, λ=254 nm, column temperature 30° C., mobile phase: a mixture of 200 ml tetrabutylammonium bromide solution (prepared from 400 mg tetrabutylammonium bromide in 1 liter of demineralized water), 450 ml ethanol and 1350 ml methanol. The average sulfur chain length and S2 to S10 sample components were analyzed and evaluated as described in ASTM D 6844. Example:

[0076] Comparative Example 1: Preparation of bis(triethoxysilylpropyl)disulfane

[0077] To prepare bis(triethoxysilylpropyl)disulfane by phase transfer catalysis, sodium carbonate (189 g, 1.8 mol, 1.2 eq.), sodium hydrosulfide (225 g, 1.6 mol, 1.0 eq., 40.0% aqueous solution) and water (572 g, 32 mol, 21 eq.) were heated to 72°C. The reaction mixture was first stirred at 72°C for 10 min, then sulfur (55 g, 1.7 mol, 1.1 eq.) was added to the mixture, which was stirred at 72°C for another 45 min. Tetra-n-butylammonium bromide (20 g, 0.03 mol, 0.02 eq., 50% aqueous solution) and (3-chloropropyl)triethoxysilane (743 g, 3.1 mol, 2.0 eq.) were added to the reaction mixture in sequence at 70-80°C. The suspension was stirred at 75°C for 3 h (GC conversion after 1 h = 98%). After the reaction is complete, water (589 g) is added and the phases are separated at 71° C. The crude product (793 g) is obtained as a yellow liquid. The low boilers are then removed by thin-film evaporator at 140° C. and 10 mbar absolute pressure, whereby bis(triethoxysilylpropyl)disulfane is isolated as the bottom product and subsequently filtered.

[0078] Comparative Example 2: Preparation of bis(triethoxysilylpropyl)tetrasulfane

[0079] To prepare bis(triethoxysilylpropyl)tetrasulfane by phase transfer catalysis, a mixture of sodium hydroxide (81 g, 1.0 mol, 1.0 equiv), sodium hydrosulfide (284 g, 2.0 mol, 2.0 equiv, 40.0% aqueous solution) and water (158 g, 8.8 mol, 4.2 equiv) was heated to 70°C. The reaction mixture was first stirred at 70°C for 10 min, then sulfur (184 g, 5.7 mol, 2.8 equiv) was added to the mixture, which was stirred for another 15 min at 72°C. Tetra-n-butylammonium bromide (17 g, 0.03 mol, 0.01 equiv, 50% aqueous solution) and (3-chloropropyl)triethoxysilane (999 g, 4.2 mol, 2.0 equiv) were added to the reaction mixture in sequence at 70-80°C. The suspension was stirred at 75°C for 2 h (GC conversion after 2 h = 98%). After the reaction was over, water (249 g) was added and the phases were separated at 71° C. The crude product (1.1 kg) was obtained as a yellow liquid. The low boilers were then removed by thin-film evaporator at 140° C. and 10 mbar absolute pressure, whereby bis(triethoxysilylpropyl)tetrasulfane was separated as the bottom product and subsequently filtered.

[0080] Example 1: Supported Steam Distillation of Bis(triethoxysilylpropyl)disulfane

[0081] Bis(triethoxysilylpropyl)disulfane from Comparative Example 1 was preheated to 97° C. and applied at 30 ml / min to the top of the column which had been heated to 160° C. and evacuated to 20 mbar absolute. Water vapor and nitrogen were fed in countercurrent from the lower part of the column and removed by distillation in the upper part of the column via a distillation system. The distillate was enriched in tributylamine, and bis(triethoxysilylpropyl)disulfane was isolated as a purified bottom product.

[0082] Column details: Filling height 75cm, inner diameter = 25mm,

[0083] Filled with porcelain saddle (6mm diameter)

[0084] GC before distillation: 0.54% tributylamine (degradation product of PTC catalyst)

[0085] GC after distillation: 0.01% tributylamine

[0086] Example 2: Supported Steam Distillation of Bis(triethoxysilylpropyl)tetrasulfane

[0087] Bis(triethoxysilylpropyl)tetrasulfane from Comparative Example 2 was preheated to 97° C. and applied at 30 ml / min to the top of the column which had been heated to 160° C. and evacuated to 20 mbar absolute. Water vapor and nitrogen were fed in countercurrent from the lower part of the column and removed by distillation in the upper part of the column via a distillation system. The distillate was enriched in tributylamine, and bis(triethoxysilylpropyl)tetrasulfane was isolated as a purified bottom product.

[0088] Column details: Filling height 75cm, inner diameter = 25mm,

[0089] Filled with porcelain saddle (6mm diameter)

[0090] GC before distillation: 0.33% tributylamine (degradation product of PTC catalyst)

[0091] GC after distillation: <0.01% tributylamine

[0092] Example 3: Supported Steam Distillation of Bis(triethoxysilylpropyl)disulfane

[0093] Batches of bis(triethoxysilylpropyl)disulfane prepared according to Comparative Example 1 were preheated to 120° C. and applied from the top at 20 kg / h to a column which had been heated to 120° C. and evacuated to an absolute pressure of 35 mbar. Water vapor (4 kg / h) and nitrogen (1 l (STP) / min) were fed in countercurrent from the lower part of the column and removed by distillation in the upper part of the column by a distillation system. The distillate was rich in tributylamine, and bis(triethoxysilylpropyl)disulfane was separated as a purified bottom product.

[0094] Column details: A DN80 distillation column was used: 4 x 1 m glass column sections with compensation heating, packed with Montz A3-500 fabric packing.

[0095] GC before distillation: 0.56% tributylamine (degradation product of PTC catalyst)

[0096] GC after distillation: <0.01% tributylamine

[0097] Example 4: Supported Steam Distillation of Bis(triethoxysilylpropyl)tetrasulfane

[0098] Batches of bis(triethoxysilylpropyl)tetrasulfane prepared according to Comparative Example 2 were preheated to 140° C. and applied from the top at 25 kg / h to a column which had been heated to 140° C. and evacuated to an absolute pressure of 35 mbar. Water vapor (3 kg / h) and nitrogen (0.5 l (STP) / min) were fed in countercurrent from the lower part of the column and removed by distillation in the upper part of the column by a distillation system. The distillate was rich in tributylamine, and bis(triethoxysilylpropyl)tetrasulfane was separated as a purified bottom product.

[0099] Column details: DN80 distillation column: 4x 1m glass column sections with compensation heating, packed with Montz A3-500 fabric packing.

[0100] GC before distillation: 0.38% tributylamine (degradation product of PTC catalyst)

[0101] GC after distillation: <0.01% tributylamine

[0102] Example 5: Ozone treatment of bis(triethoxysilylpropyl)disulfane

[0103] 150 g of bis(triethoxysilylpropyl)disulfane from Comparative Example 1 were charged to a 250 ml bottle-shaped reaction apparatus and stirred at room temperature. An ozone / air mixture produced in an ozone generator was passed through the crude product via a hose over a period of 2 hours, the mixture having an ozone component of about 260 mg of ozone. Low boilers were then removed by a thin-film evaporator at 140° C. and 13 mbar absolute pressure, whereby bis(triethoxysilylpropyl)disulfane was isolated as a bottom product.

[0104] Output of ozone generator: about 130mg / h in air

[0105] GC before ozone treatment: 0.1% ethanol, 0.16% tributylamine (degradation product of PTC catalyst)

[0106] GC after ozone treatment: 0.1% ethanol, <0.01% tributylamine

[0107] GC after thin film evaporator: 0.02% ethanol, <0.01% tributylamine

[0108] Example 6: Ozone treatment of bis(triethoxysilylpropyl)tetrasulfane

[0109] A 250 ml bottle-shaped reaction apparatus was charged with 150 g of bis(triethoxysilylpropyl)tetrasulfane from Comparative Example 2 and stirred at room temperature. An ozone / air mixture produced in an ozone generator was passed through the crude product via a hose over a period of 1 hour, the mixture having an ozone component of about 130 mg of ozone. Low boilers were then removed by a thin-film evaporator at 140° C. and 13 mbar absolute pressure, whereby bis(triethoxysilylpropyl)tetrasulfane was isolated as a bottom product.

[0110] Output of ozone generator: about 130mg / h in air

[0111] GC before ozone treatment: 0.2% ethanol, 0.15% tributylamine (degradation product of PTC catalyst)

[0112] GC after ozone treatment: 0.04% ethanol, <0.01% tributylamine

[0113] GC after thin film evaporator: 0.03% ethanol, <0.01% tributylamine

[0114] Example 7: Activated carbon treatment of bis(triethoxysilylpropyl)disulfane

[0115] Bis(triethoxysilylpropyl)disulfane was treated by steam distillation of the support according to the process of the invention according to Example 1. In a subsequent step, the bis(triethoxysilylpropyl)disulfane from Example 1 was mixed with 1% or 2% of activated carbon, respectively, at room temperature and then filtered.

[0116] GC before activated carbon: 0.01% tributylamine

[0117] GC after 1% activated carbon: <0.01% tributylamine

[0118] GC after 2% activated carbon: <0.01% tributylamine

[0119] Example 8: Activated carbon treatment of bis(triethoxysilylpropyl)tetrasulfane

[0120] Bis(triethoxysilylpropyl)tetrasulfane was processed by steam distillation according to the distillation according to the invention according to the carrier of Example 2. In a subsequent step, the bis(triethoxysilylpropyl)tetrasulfane from Example 2 was mixed with 1% or 2% of activated carbon at room temperature and then filtered.

[0121] GC before activated carbon: 0.01% tributylamine

[0122] GC after 1% activated carbon: <0.01% tributylamine

[0123] GC after 2% activated carbon: <0.01% tributylamine

[0124] Example 9: Stability test of bis(triethoxysilylpropyl)tetrasulfane containing 0.28% tributylamine:

[0125] An extended storage stability test was performed for Comparative Example 2. Bis(triethoxysilylpropyl)tetrasulfane was analyzed by HPLC at specified time intervals. The content of S2 and S3 as prepared was unstable.

[0126] HPLC after about 1 day: S2 content: 17 wt %; S3 content: 31 wt %; S4-S10 content: 52 wt %.

[0127] HPLC after about 7 months: S2 content: 16 wt %; S3 content: 32 wt %; S4-S10 content: 52 wt %.

[0128] HPLC after about 15 months: S2 content: 15 wt %; S3 content: 33 wt %; S4-S10 content: 52 wt %.

[0129] Example 10: Stability test of bis(triethoxysilylpropyl)tetrasulfane containing <0.01% tributylamine:

[0130] The extended storage stability test was performed on Inventive Example 2. Bis(triethoxysilylpropyl)tetrasulfane was analyzed by HPLC at specified time intervals. The content of S2 and S3 as prepared was stable.

[0131] HPLC after about 1 day: S2 content: 18 wt %, S3 content: 31 wt %, S4-S10 content: 51 wt %.

[0132] HPLC after about 1 month: S2 content: 18 wt %; S3 content: 31 wt %; S4-S10 content: 51 wt %.

[0133] HPLC after about 6 months: S2 content: 18 wt %, S3 content: 31 wt %, S4-S10 content: 51 wt %.

[0134] Example 11: Stability test of bis(triethoxysilylpropyl)tetrasulfane containing <0.01% tributylamine:

[0135] The extended storage stability test was performed on Inventive Example 5. Bis(triethoxysilylpropyl)tetrasulfane was analyzed by HPLC at specified time intervals. The content of S2 and S3 as prepared was stable.

[0136] HPLC after about 1 day: S2 content: 17 wt %, S3 content: 31 wt %, S4-S10 content: 52 wt %.

[0137] HPLC after about 5 months: S2 content: 17 wt %, S3 content: 31 wt %, S4-S10 content: 52 wt %.

[0138] HPLC after about 23 months: S2 content: 17 wt %, S3 content: 31 wt %, S4-S10 content: 52 wt %.

Claims

1. A method for preparing polysulfane silane of formula I (R 1 ) 3-m R 2 m Si-R 3 -S x -R 3 -SiR 2 m (R 1 ) 3-m I Where R 1 The same or different and are C1-C10 alkoxy, phenoxy, R 2 are the same or different and are C6-C20 aryl, C1-C10 alkyl, C7-C20 aralkyl, R 3 the same or different and branched or unbranched, saturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C1-C30 hydrocarbon radicals, and m is the same or different and is 0, 1, 2 or 3, x is 2-10, The method comprises the following steps: in the presence of a base, an aqueous phase and a phase transfer catalyst of formula III Where Y is N, R 4 , R 5 , R 6 and R 7 The same or different and are -(CH2) k CH3 alkyl, wherein k = 0-9, or in the group consisting of R 4 , R 5 , R 6 and R 7 There is one or two ring closures between the two substituents of the group -(CH2) n -, where n = 2-5, and X - F - ,I - , Cl - Br - , At least one silane of formula II (R 1 ) 3-m R 2 m Si-R 3 - Hall II Where Hal is Cl, Br or I, Reacts with sodium hydrosulfide, potassium hydrosulfide and / or sulfur, The base used is M 3-w CO3, M(OH) w , where w is 1, and M = Na or K, It is characterized in that During or after the reaction, at least one steam distillation and / or ozone treatment of the carrier is performed to remove tributylamine, a degradation product of the phase transfer catalyst.

2. The method for preparing polysulfanesilane of formula I according to claim 1, characterized in that R 1 is ethoxy, m=0 and R 3 =(CH2)3.

3. The process for preparing polysulfanesilane of formula I according to claim 1, wherein n=4.

4. The method for preparing polysulfanesilane of formula I according to claim 1 or 2, characterized in that Hal=Cl.

5. The method for preparing polysulfanesilane of formula I according to claim 1, characterized in that The base used is Na2CO3 or NaOH.

6. The method for preparing polysulfanesilane of formula I according to claim 1, characterized in that The reaction is carried out at a temperature of 25°C to 200°C.

7. The method for preparing polysulfanesilane of formula I according to claim 1, characterized in that A phase transfer catalyst of formula III and a silane of formula II are added to the aqueous phase.

8. The method for preparing polysulfanesilane of formula I according to claim 1, characterized in that Additionally, charcoal post-treatment was performed.

9. The method for preparing polysulfanesilane of formula I according to claim 1, characterized in that Sodium hydrosulfide and potassium hydrosulfide are prepared in situ from NaOH, KOH and sulfur.

10. Use of steam distillation and / or ozone treatment of a support for removing degradation products of a phase transfer catalyst in a process according to any one of claims 1 to 9.

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