# Patent

## Title
Process for preparing mercaptoorganyl (alkoxysilanes)

## Abstract

The present invention relates to a process for preparing mercaptoorganyl(alkoxysilanes), by hydrogenating bis(alkoxy-silylorganyl) polysulphides with hydrogen in the presence of at least one alcohol and a doped metal catalyst. The doped metal catalyst comprises at least one substance from the group consisting of iron, iron compound, nickel, nickel compound, palladium, palladium compound, osmium, osmium compound, ruthenium, ruthenium compound, rhodium, rhodium compound, iridium and iridium compound plus at least one doping component.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
The present application claims priority to German application DE 10 20052 020 535.6, filed on May 3, 2005, the contents of which is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to a process for preparing mercaptoorganyl(alkoxysilanes).
BACKGROUND OF THE INVENTION
U.S. Pat. No. 6,433,206 discloses a process for preparing silicon-containing organomercaptans by hydrogenating bis(organyl-silyl) polysulphides using group VIII metal catalysts which must be preserved from poisoning by water, H2S or alcohols. That process has the drawback that the conversion (“g of product silane” per “minute” per “mmol of catalyzing metal”) under energy-sparing conditions is relatively low. The known reaction proceeds with satisfactory conversion only under high pressure and temperature conditions (>100 bar and >180° C.) which are difficult to realise technically, owing to the high load on the material for the plant.
DE 102004043094.2 discloses a process for preparing mercaptoorganyl(alkoxysilanes) that involves hydrogenating bis(alkoxysilylorganyl) polysulphides at temperatures of <190° C. and pressures of <100 bar with hydrogen and a transition metal catalyst and without adding water, alcohol or H2S.
DE 102004043093.4, furthermore, discloses a process for preparing mercaptoorganyl(alkoxysilanes) that involves hydrogenating bis(alkoxysilylorganyl) polysulphides in a solvent with hydrogen and a transition metal catalyst without any alcohols, H2S or water.


DESCRIPTION OF THE INVENTION
It is an object of the present invention to provide a process for the reductive cleavage of bis(alkoxysilylorganyl) polysulphides that permits at least equal conversions under milder temperature and/or pressure conditions than the process known from U.S. Pat. No. 6,433,206.
The invention provides a process for preparing mercaptoorganyl(alkoxysilanes), by hydrogenating bis(alkoxy-silylorganyl) polysulphides with hydrogen in the presence of at least one alcohol and a doped metal catalyst, characterized in that the doped metal catalyst comprises at least one substance from the group consisting of iron, iron compound, nickel, nickel compound, palladium, palladium compound, osmium, osmium compound, ruthenium, ruthenium compound, rhodium, rhodium compound, iridium and iridium compound plus at least one doping component.
The bis(alkoxysilylorganyl) polysulphide may be in solution in the alcohol and may be a compound of the general formula (I):

Z-A-Sx-A-Z  (I)

in which x is a number from 1 to 14, preferably 1 to 8, more preferably 2 to 4, very preferably 2.0-2.6 and 3.2-3.9, Z is identical or different at each occurrence and is SiX1X2X3 or Si(OCH2—CH2—)3N

where X1, X2 and X3 each independently of one another can be a linear, branched or cyclic hydrocarbon chain having 1-18 carbon atoms (C1-C18), preferably having 1-10 carbon atoms (C1-C10), more preferably methyl, ethyl, propyl or butyl, a linear or branched alkyl acid group (CaH2a+1)—C(═O)O— with a=1-25, such as acetoxy-CH3—(C═O)O—, a linear or branched alkenyl acid substituent (CbH2b−1)—C(═O)O— with b=2-25, a linear or branched, substituted alkyl or alkenyl acid group, an unsubstituted, halogen-substituted or alkyl-substituted cycloalkane radical having 5-12 carbon atoms, a benzyl radical, a halogen-substituted or alkyl-substituted phenyl radical, alkoxy groups with linear and/or branched hydrocarbon chains, preferably (C1-C24)alkoxy, more preferably methoxy-(CH3O—), ethoxy-C2H5O—), propoxy-(C3H7O), butoxy-(C4H9O—), dodecyloxy-(C12H25O—), tetradecyloxy-(C14H29O—), hexadecyloxy-(C16H33O—) or octadecyloxy-(C18H37O—), a cycloalkoxy group having 5-12 carbon atoms, cyclohexanol for example, a halogen-substituted or alkyl-substituted phenoxy group or a benzyloxy group, an alkyl ether group O— (CRI2—CRI2)—O-Alk or alkyl polyether group O—(CRI2—CRI2O)y— Alk, with y=2-25, preferably y=2-15, more preferably y=3-10, very preferably y=3-6, RI independently at each occurrence is H or an alkyl group, preferably a CH3 group, Alk is a linear or branched, saturated or unsaturated alkyl chain having 1-30 carbon atoms (C1-C30), preferably C1-C20, more preferably C4-C18, very preferably C8-C16, and

A is a linear or branched, saturated or unsaturated aliphatic, aromatic or mixedly aliphatic/aromatic divalent C1-C30 hydrocarbon chain, preferably C1-C4, more preferably (—CH2—), (—CH2—)2, (—CH2—)3, (—CH(CH3)—CH2—), (—CH2—CH(CH3)—), (—CH2—CH2—CH(CH3)—) or (—CH2—CH(CH3)—CH2—).

The alkyl polyether group may include ethylene oxide (CH2—CH2—O) and propylene oxide (CH(CH3)—CH2—O) or (CH2—CH(CH3)—O) units, distributed randomly or in blocks. The alkyl polyether group O—(CRI2—CRI2O)y-Alk may be O—(CH2—CH2O)2—C8H17, O—(CH2—CH2O)3—C8H17, O—(CH2—CH2O)4—C8H17, O—(CH2—CH2O)5—C8H17, O—(CH2—CH2O)6—C8H17, O—(CH2—CH2O)7—C8H17, O—(CH(CH3)—CH2O)2—C8H17, O—(CH(CH3)—CH2O)3—C8H17, O—(CH(CH3)—CH2O)4—C8H17, O—(CH(CH3)—CH2O)5—C8H17, O—(CH(CH3)—CH2O)6—C8H17, O—(CH(CH3)—CH2O)7—C8H17, O—(CH2—CH2O)2—C9H19, O—(CH2—CH2O)3—C9H19, O—(CH2—CH2O)4—C9H19, O—(CH2—CH2O)5—C9H19, O—(CH2—CH2O)6—C9H19, O—(CH2—CH2O)7—C9H19, O—(CH(CH3)—CH2O)2—C9H19, O—(CH(CH3)—CH2O)3—C9H19, O—(CH(CH3)—CH2O)4—C9H19, O—(CH(CH3)—CH2O)5—C9H19, O—(CH(CH3)—CH2O)6—C9H19, O—(CH(CH3)—CH2O)7—C9H19, O—(CH2—CH2O)2—C10H21, O—(CH2—CH2O)3—C10H21, O—(CH2—CH2O)4—C10H21, O—(CH2—CH2O)5—C10H21, O—(CH2—CH2O)6—C10H21, O—(CH2—CH2O)7—C10H21, O—(CH(CH3)—CH2O)2—C10H21, O—(CH(CH3)—CH2O)3—C10H21, O—(CH(CH3)—CH2O)4—C10H21, O—(CH(CH3)—CH2O)5—C10H21, O—(CH(CH3)—CH2O)6—C10H21, O—(CH(CH3)—CH2O)7—C10H21, O—(CH2—CH2O)2—C11H23, O—(CH2—CH2O)3—C11H23, O—(CH2—CH2O)4—C11H23, O—(CH2—CH2O)5—C11H23, O—(CH2—CH2O)6—C11H23, O—(CH2—CH2O)7—C11H23, O—(CH(CH3)—CH2O)2—C11H23, O—(CH(CH3)—CH2O)3—C11H23, O—(CH(CH3)—CH2O)4—C11H23, O—(CH(CH3)—CH2O)5—C11H23, O—(CH(CH3)—CH2O)6—C11H23, O—(CH(CH3)—CH2O)7—C11H23, O—(CH2—CH2O)2—C12H25, O—(CH2—CH2O)3—C12H25, O—(CH2—CH2O)4—C12H25, O—(CH2—CH2O)5—C12H25, O—(CH2—CH2O)6—C12H25, O—(CH2—CH2O)7—C12H25, O—(CH(CH3)—CH2O)2—C12H25, O—(CH(CH3)—CH2O)3—C12H25, O—(CH(CH3)—CH2O)4—C12H25, O—(CH(CH3)—CH2O)5—C12H25, O—(CH(CH3)—CH2O)6—C12H25, O—(CH(CH3)—CH2O)7—C12H25, O—(CH2—CH2O)2—C13H27, O—(CH2—CH2O)3—C13H27, O—(CH2—CH2O)4—C13H27, O—(CH2—CH2O)5—C13H27, O—(CH2—CH2O)6—C13H27, O—(CH2—CH2O)7—C13H27, O—(CH(CH3)—CH2O)2—C13H27, O—(CH(CH3)—CH2O)3—C13H27, O—(CH(CH3)—CH2O)4—C13H27, O—(CH(CH3)—CH2O)5—C13H27, O—(CH(CH3)—CH2O)6—C13H27, O—(CH(CH3)—CH2O)7—C13H27, O—(CH2—CH2O)2—C14H29, O—(CH2—CH2O)3—C14H29, O—(CH2—CH2O)4—C14H29, O—(CH2—CH2O)5—C14H29, O—(CH2—CH2O)6—C14H29, O—(CH2—CH2O)7—C14H29, O—(CH(CH3)—CH2O)2—C14H29, O—(CH(CH3)—CH2O)3—C14H29, O—(CH(CH3)—CH2O)4—C14H29, O—(CH(CH3)—CH2O)5—C14H29, O—(CH(CH3)—CH2O)6—C14H29, O—(CH(CH3)—CH2O)7—C14H29, O—(CH2—CH2O)2—C15H31, O—(CH2—CH2O)3—C15H31, O—(CH2—CH2O)4—C15H31, O—(CH2—CH2O)5—C15H31, O—(CH2—CH2O)6—C15H31, O—(CH2—CH2O)7—C15H31, O—(CH(CH3)—CH2O)2—C15H31, O—(CH(CH3)—CH2O)3—C15H31, O—(CH(CH3)—CH2O)4—C15H31, O—(CH(CH3)—CH2O)5—C15H31, O—(CH(CH3)—CH2O)6—C15H31, O—(CH(CH3)—CH2O)7—C15H31, O—(CH2—CH2O)2—C16H33, O—(CH2—CH2O)3—C16H33, O—(CH2—CH2O)4—C16H33, O—(CH2—CH2O)5—C16H33, O—(CH2—CH2O)6—C16H33, O—(CH2—CH2O)7—C16H33, O—(CH(CH3)—CH2O)2—C16H33, O—(CH(CH3)—CH2O)3—C16H33, O—(CH(CH3)—CH2O)4—C16H33, O—(CH(CH3)—CH2O)5—C16H33, O—(CH(CH3)—CH2O)6—C16H33 or O—(CH(CH3)—CH2O)7—C16H33.
A may be linear or branched and may contain saturated and unsaturated bonds. A may be substituted by, instead of H, any of a very wide variety of substituents, independently of one another, such as, for example, —CN, —SH, —NH2, halogens, for example —Cl, —Br or —F, alcohol functionalities —OH or Alkoxides —O-alkyl. As A it is possible to use CH2, CH2CH2, CH2CH2CH2, CH2CH(CH3), CH2CH2CH2CH2, CH2CH2CH(CH3), CH2CH(CH3)CH2, CH2CH2CH2CH2CH2, CH2CH(CH3)CH2CH2, CH2CH2CH(CH3)CH2, CH(CH3)CH2CH(CH3) or CH2CH(CH3)CH(CH3).
As the silane of the general formula (I) it is possible to use, for example, the following compounds:

    [(MeO)3Si(CH2)3]2S2, [(MeO)3Si(CH2)3]2S3, [(MeO)3Si(CH2)3]2S4, [(MeO)3Si(CH2)3]2S5, [(MeO)3Si(CH2)3]2S6, [(MeO)3Si(CH2)3]2S7, [(MeO)3Si(CH2)3]2S8, [(MeO)3Si(CH2)3]2S9, [(MeO)3Si(CH2)3]2S10, [(MeO)3Si(CH2)3]2S11, [(MeO)3Si(CH2)3]2S12, [(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, [(EtO)3Si(CH2)3]2S10, [(EtO)3Si(CH2)3]2S11, [(EtO)3Si(CH2)3]2S12, [(EtO)3Si(CH2)3]2S13, [(EtO)3Si(CH2)3]2S14, [(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]2S10, [(C3H7O)3Si(CH2)3]2S11, [(C3H7O)3Si(CH2)3]2S12, [(C3H7O)3Si(CH2)3]2S13, [(C3H7O)3Si(CH2)3]2S14, [(C12H25O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C12H25O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C12H25O)3Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C12H25O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C12H25O)(OEt)2], [(C12H25O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C12H25O)(OEt)2], [(C12H25O)3Si(CH2)3]Sx[(CH2)3Si(C12H25O)(OEt)2], [(C12H25O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C12H25O)2(OEt)], [(C12H25O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C12H25O)2(OEt)], [(C12H25O)3Si(CH2)3]Sx[(CH2)3Si(C12H25O)2(OEt)], [(C12H25O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C12H25O)3], [(C12H25O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C12H25O)3], [(C12H25O)3Si(CH2)3]Sx[(CH2)3Si(C12H25O)3], [(C14H29O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C14H29O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C14H29O)3Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C14H29O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C14H29O)(OEt)2], [(C14H29O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C14H29O)(OEt)2], [(C14H29O)3Si(CH2)3]Sx[(CH2)3Si(C14H29O)(OEt)2], [(C14H29O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C14H29O)2(OEt)], [(C14H29O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C14H29O)2(OEt)], [(C14H29O)3Si(CH2)3]Sx[(CH2)3Si(C14H29O)2(OEt)], [(C14H29O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C14H29O)3], [(C14H29O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C14H29O)3], [(C14H29O)3Si(CH2)3]Sx[(CH2)3Si(C14H29O)3], [(C16H33O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C16H33O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C16H33O)3Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C16H33O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C16H33O)(OEt)2], [(C16H33O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C16H33O)(OEt)2], [(C16H33O)3Si(CH2)3]Sx[(CH2)3Si(C16H33O)(OEt)2], [(C16H33O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C16H33O)2(OEt)], [(C16H33O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C16H33O)2(OEt)], [(C16H33O)3Si(CH2)3]Sx[(CH2)3Si(C16H33O)2(OEt)], [(C16H33O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C16H33O)3], [(C16H33O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C16H33O)3], [(C16H33O)3Si(CH2)3]Sx[(CH2)3Si(C16H33O)3], [(C18H37O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C18H37O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C18H37O)3Si(CH2)3]Sx[(CH2)3Si(OEt)3], [(C18H37O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C18H37O)(OEt)2], [(C18H37O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C18H37O)(OEt)2], [(C18H37O)3Si(CH2)3]Sx[(CH2)3Si(C18H37O)(OEt)2], [(C18H37O)(EtO)2Si(CH2)3]S[(CH2)3Si(C18H37O)2(OEt)], [(C18H37O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C18H37O)2(OEt)], [(C18H37O)3Si(CH2)3]Sx[(CH2)3Si(C18H37O)2(OEt)], [(C18H37O)(EtO)2Si(CH2)3]Sx[(CH2)3Si(C18H37O)3], [(C18H37O)2(EtO)Si(CH2)3]Sx[(CH2)3Si(C18H37O)3], [(C18H37O)3Si(CH2)3]Sx[(CH2)3Si(C18H37O)3]


The bis(alkoxysilylorganyl) polysulphide starting materials used may be a mixture of different bis(alkoxysilylorganyl) polysulphides with —S1— to —S14— (x=1-14) or a single bis(alkoxysilylorganyl) polysulphide with x=2-14.
Bis(alkoxysilylorganyl) polysulphides used may be compounds or mixtures of compounds having an average sulphur chain length of 2.0 to 4.0. The average sulphur chain length for bis(alkoxysilylorganyl) polysulphides may be determined as an arithmetic mean of S2 to S14, measured by HPLC. Preferably compounds have an average chain length of Sx=S2.0 to S2.6 and Sx=S3.2 to S3.9. Particularly preferred are bis(alkoxysilylorganyl) disulphides having an average chain length of 2.0 to 2.6, since in comparison to bis(alkoxysilylorganyl) polysulphides with Sx=S2.7 to S3.9 it is possible to achieve higher conversions in g product/min/mmol catalyst and for less H2S to be released.
The group Z=—SiX1X2X3 in formula I can with preference be —Si(OMe)3, —Si(OEt)3, —SiMe(OMe)2, —SiMe(OEt)2), —SiMe2(OMe) —SiMe2(OEt), —Si[—O(CO)CH3]3, —Si(OC12H25)3, Si(OC14H29)3, Si(OC16H33)3, Si(OC18H37)3, Si(OC14H29)2(OC16H33), Si(OC14H29)2(OC18H37), Si(OC16H33)2(OC14H29), Si(OC16H33)2 (OC18H37), Si(OC18H37)2(OC16H33) or Si(OC14H29)(OC18H37)2.
The mercaptoorganyl(alkoxysilane) product may be a compound of the general formula (II)

W-A-SH  (II)

wherein W=—SiY1Y2Y3 or Si(OCH2—CH2—)3N, with Y1, Y2 and Y3 independently of one another able to be X1, X2, X3 or hydroxyl (—OH) and with X1, X2, X3 and A, in each case independently of one another, having the definition as per formula (I).

The group W=—SiY1Y2Y3 in formula II may with preference be —Si(OMe)3, —Si(OMe)2OH, —Si(OMe) (OH)2, —Si(OEt)3, —Si(OEt)2OH, —Si(OEt) (OH)2, —SiMe(OMe)2, —SiMe(OEt)2), —SiMe(OH)2, —SiMe2(OMe), —SiMe2(OEt), SiMe2(OH), —Si[—O(CO)CH3]3, —Si(OC12H25)3, Si(OC14H29)3, Si(OC16H33)3, Si(OC18H37)3, Si(OC14H29)2 (OC16H33), Si(OC14H29)2 (OC18H37), Si(OC16H33)2 (OC14H29), Si(OC16H33)2 (OC18H37), Si(OC18H37)2 (OC16H33) or Si(OC14H29) (OC18H37)2.
Mercaptoorganyl(alkoxysilanes) of the general formula (II) may for example be the following:

    3-mercaptopropyl(trimethoxysilane), 3-mercaptopropyl(dimethoxyhydroxysilane), 3-mercaptopropyl(triethoxysilane), 3-mercaptopropyl(diethoxyhydroxysilane), 3-mercaptopropyl(diethoxymethoxysilane), 3-mercaptopropyl(tripropoxysilane), 3-mercaptopropyl(dipropoxymethoxysilane), 3-mercaptopropyl(dipropoxyhydroxysilane), 3-mercaptopropyl(tridodecanoxysilane), 3-mercaptopropyl(didodecanoxyhydroxysilane), 3-mercaptopropyl(tritetradecanoxysilane), 3-mercaptopropyl(trihexadecanoxysilane), 3-mercaptopropyl(trioctadecanoxysilane), 3-mercaptopropyl(didodecanoxy)tetradecanoxysilane, 3-mercaptopropyl(dodecanoxy)tetradecanoxy(hexadecanoxy) silane, 3-mercaptopropyl(dimethoxymethylsilane), 3-mercaptopropyl(methoxymethylhydroxysilane), 3-mercaptopropyl(methoxydimethylsilane), 3-mercaptopropyl(hydroxydimethylsilane), 3-mercaptopropyl(diethoxymethylsilane), 3-mercaptopropyl(ethoxyhydroxymethylsilane), 3-mercaptopropyl(ethoxydimethylsilane), 3-mercaptopropyl(dipropoxymethylsilane), 3-mercaptopropyl(propoxymethylhydroxysilane), 3-mercaptopropyl(propoxydimethylsilane), 3-mercaptopropyl(diisopropoxymethylsilane), 3-mercaptopropyl(isopropoxydimethylsilane), 3-mercaptopropyl(dibutoxymethylsilane), 3-mercaptopropyl(butoxydimethylsilane), 3-mercaptopropyl(disiobutoxymethylsilane), 3-mercaptopropyl(siobutoxymethylhydroxysilane), 3-mercaptopropyl(isobutoxydimethylsilane), 3-mercaptopropyl(didodecanoxymethylsilane), 3-mercaptopropyl(dodecanoxydimethylsilane), 3-mercaptopropyl(ditetradecanoxymethylsilane), 3-mercaptopropyl(tetradecanoxymethylhydroxysilane), 3-mercaptopropyl(tetradecanoxydimethylsilane), 2-mercaptoethyl(trimethoxysilane), 2-mercaptoethyl(triethoxysilane), 2-mercaptoethyl(diethoxymethoxysilane), 2-mercaptoethyl(tripropoxysilane), 2-mercaptoethyl(dipropoxymethoxysilane), 2-mercaptoethyl(tridodecanoxysilane), 2-mercaptoethyl(tritetradecanoxysilane), 2-mercaptoethyl(trihexadecanoxysilane), 2-mercaptoethyl(trioctadecanoxysilane), 2-mercaptoethyl(didodecanoxy)tetradecanoxysilan, 2-mercaptoethyl(dodecanoxy)tetradecanoxy(hexadecanoxy) silane, 2-mercaptoethyl(dimethoxymethylsilane), 2-mercaptoethyl(methoxymethylhydroxysilane), 2-mercaptoethyl(methoxydimethylsilane), 2-mercaptoethyl(diethoxymethylsilane), 2-mercaptoethyl(ethoxydimethylsilane), 2-mercaptoethyl(hydroxydimethylsilane), 1-mercaptomethyl(trimethoxysilane), 1-mercaptomethyl(triethoxysilane), 1-mercaptomethyl(diethoxymethoxysilane), 1-mercaptomethyl(diethoxyhydroxysilane), 1-mercaptomethyl(dipropoxymethoxyslane), 1-mercaptomethyl(tripropoxysilane), 1-mercaptomethyl(trimethoxysilane), 1-mercaptomethyl(dimethoxymethylsilane), 1-mercaptomethyl(methoxydimethylsilane), 1-mercaptomethyl(diethoxymethylsilane), 1-mercaptomethyl(ethoxymethylihydroxysilane), 1-mercaptomethyl(ethoxydimethylsilane), 3-mercaptobutyl(trimethoxysilane), 3-mercaptobutyl(triethoxysilane), 3-mercaptobutyl(diethoxymethoxysilane) 3-mercaptobutyl(tripropoxysilane), 3-mercaptobutyl(dipropoxymethoxysilane), 3-mercaptobutyl(dimethoxymethylsilane), 3-mercaptobutyl(diethoxymethylsilane), 3-mercaptobutyl(dimethylmethoxysilane), 3-mercaptobutyl(dimethylethoxysilane), 3-mercaptobutyl(dimethyhydroxysilane), 3-mercaptobutyl(tridodecanoxysilane), 3-mercaptobutyl(tritetradecanoxysilane), 3-mercaptobutyl(trihexadecanoxysilane), 3-mercaptobutyl(didodecanoxy)tetradecanoxysilan, 3-mercaptobutyl(dodecanoxy)tetradecanoxy(hexadecanoxy) silane, 3-mercapto-2-methyl-propyl(trimethoxysilane), 3-mercapto-2-methyl-propyl(triethoxysilane), 3-mercapto-2-methyl-propyl(diethoxymethoxysilane), 3-mercapto-2-methyl-propyl(tripropoxysilane), 3-mercapto-2-methyl-propyl(dipropoxymethoxysilane), 3-mercapto-2-methyl-propyl(tridodecanoxysilane), 3-mercapto-2-methyl-propyl(tritetradecanoxysilane), 3-mercapto-2-methyl-propyl(trihexadecanoxysilane), 3-mercapto-2-methyl-propyl(trioctadecanoxysilane), 3-mercapto-2-methyl-propyl(didodecanoxy)tetradecanoxysilane, 3-mercapto-2-methyl-propyl(dodecanoxy)tetradecanoxy-(hexadecanoxy)silane, 3-mercapto-2-methyl-propyl(dimethoxymethylsilane), 3-mercapto-2-methyl-propyl(methoxydimethylsilane), 3-mercapto-2-methyl-propyl(diethoxymethylsilane), 3-mercapto-2-methyl-propyl(ethoxydimethylsilane), 3-mercapto-2-methyl-propyl(hydroxydimethylsilane), 3-mercapto-2-methyl-propyl(dipropoxymethylsilane), 3-mercapto-2-methyl-propyl(propoxydimethylsilane), 3-mercapto-2-methyl-propyl(diisopropoxymethylsilane), 3-mercapto-2-methyl-propyl(isopropoxydimethylsilane), 3-mercapto-2-methyl-propyl(dibutoxymethylsilane), 3-mercapto-2-methyl-propyl(butoxydimethylsilane), 3-mercapto-2-methyl-propyl(diisobutoxymethylsilane), 3-mercapto-2-methyl-propyl(isobutoxydimethylsilane), 3-mercapto-2-methyl-propyl(didodecanoxymethylsilane), 3-mercapto-2-methyl-propyl(dodecanoxydimethylsilane), 3-mercapto-2-methyl-propyl(ditetradecanoxymethylsilane), 3-mercapto-2-methyl-propyl(tetradecanoxydimethylsilane), [(C9H19O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C9H9O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C9H9O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6]2 (EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6]3Si(CH2)3SH or HS—CH2—CH2—CH2—Si(OCH2—CH2—)3N.


The alcohol can be used in a fraction of 0.01% to 95%, preferably of 0.1% to 60%, more preferably of 0.1% to 40%, very preferably of 0.1% to 30%, and with greatest preference of 1% to 5%, by weight, based on the total weight of bis(alkoxysilylorganyl) polysulphides and alcohol.
The alcohol used may be a mixture of alcohols. It may have a boiling point of 50° C. to 280° C., preferably 50-150° C., and more preferably 50-120° C. The alcohol may be a primary, secondary or tertiary alcohol, alkyl ether alcohol HO—(CRI2—CRI2)—O-Alk or alkyl polyether alcohol HO—(CRI2—CRI2O)y-Alk.
Primary, secondary or tertiary alcohols which can be used include methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, tert-butanol, dodecanol, tetradecanol, hexadecanol or octadecanol.
Alkyl polyether alcohols may be the following:

    HO—(CH2—CH2—O)2—C6H13, HO—(CH2—CH2—O)3—C6H13, HO—(CH2—CH2—O)4—C6H13, HO—(CH2—CH2—O)5—C6H13, HO—(CH2—CH2—O)6—C6H13 HO—(CH2—CH2—O)7—C6H13, HO—(CH2—CH2—O)8—C6H13, HO—(CH2—CH2—O)9—C6H13, HO—(CH2—CH2—O)2—C10H21, HO—(CH2—CH2—O)3—C10H21, HO—(CH2—CH2—O)4—C10H21, HO—(CH2—CH2—O)5—C10H21, HO—(CH2—CH2—O)6—C10H21, HO—(CH2—CH2—O)7—C10H21, HO—(CH2—CH2—O)8—C10H21, HO—(CH2—CH2—O)9—C10H21, HO—(CH2—CH2—O)2—C13H27, HO—(CH2—CH2—O)3—C13H27, HO—(CH2—CH2—O)4—C13H27, HO—(CH2—CH2—O)5—C13H27, HO—(CH2—CH2—O)6—C13H27, HO—(CH2—CH2—O)7—C13H27, HO—(CH2—CH2—O)8—C13H27, HO—(CH2—CH2—O)9—C13H27, HO—(CH2—CH2—O)2—C14H29, HO—(CH2—CH2—O)3—C14H29, HO—(CH2—CH2—O)4—C14H29, HO—(CH2—CH2—O)5—C14H29, HO—(CH2—CH2—O)6—C14H29, HO—(CH2—CH2—O)7—C14H29, HO—(CH2—CH2—O)8—C14H29, HO—(CH2—CH2—O)9—C14H29, HO—(CH2—CH2—O)2—C15H31, HO—(CH2—CH2—O)3—C15H31, HO—(CH2—CH2—O)4—C15H31, HO—(CH2—CH2—O)5—C15H31, HO—(CH2—CH2—O)6—C15H31, HO—(CH2—CH2—O)7—C15H31, HO—(CH2—CH2—O)8—C15H31 or HO—(CH2—CH2—O)9—C15H31.


The reaction can be carried out preferably with exclusion of air and water.
Prior to, during or at the end of the reaction it is possible to add additives to the reaction mixture. The additives may prolong the service life of the catalysts employed, simplify or enhance handling of the catalysts, increase the reusability of the catalysts or improve the economics of the process.
Additives may be organosulphur compounds, titanium alkoxylates, amines, water, organic or inorganic acids or bases, or mixtures of the aforementioned compounds. They may also be carboxylic acids, DMSO, monoalkylamines, dialkylamines or trialkylamines. Additives may be Ti(OC4H9)4 or Ti(OC3H7)4.
The reaction mixture may include by-products and/or impurities which have come about in an upstream process step during the preparation of the bis(alkoxysilylorganyl) polysulphides. The by-products and/or impurities may reduce the complexity and the cost and inconvenience of the overall process encompassing bis(alkoxysilylorganyl) polysulphide preparation and hydrogenation. The presence of by-products and/or impurities may be the consequence of omitting a separation step during the working-up of the bis(alkoxysilylorganyl) polysulphides used as starting material for the hydrogenation. Possible by-products and/or impurities include alkali metal halides, preferably sodium chloride and potassium chloride.
The hydrogenation can be carried out under a hydrogen overpressure of 5 to 250 bar, preferably 5 to 99 bar, more preferably 5 to 55 bar, very preferably 5 to 40 bar.
The hydrogenation may be carried out at a temperature of 50 to 250° C., preferably 75 to 189° C., more preferably 100 to 175° C., very preferably 110 to 160° C.
The time for the hydrogenation reaction may amount to less than 360 minutes, preferably less than 300 minutes, more preferably less than 240 minutes, very preferably less than 180 minutes.
The doping component of the doped metal catalyst may be at least one metal and/or at least one metal compound. The doped metal catalyst may be a mixture composed of at least one substance from the group consisting of iron, iron compound, nickel, nickel compound, palladium, palladium compound, osmium, osmium compound, ruthenium, ruthenium compound, rhodium, rhodium compound, iridium and iridium compound and of at least one metal and/or at least one metal compound, which independently of one another may be present in elemental, alloyed, chemically bonded or physically mixed form.
The substance from the group consisting of iron, iron compound, nickel, nickel compound, palladium, palladium compound, osmium, osmium compound, ruthenium, ruthenium compound, rhodium, rhodium compound, iridium and iridium compound is different from the doping component of the doped metal catalyst.
The doping component of the doped metal catalyst may be composed of at least one metal and/or at least one metal compound that differs from the substance from the group consisting of iron, iron compound, nickel, nickel compound, palladium, palladium compound, osmium, osmium compound, ruthenium, ruthenium compound, rhodium, rhodium compound, iridium and iridium compound.
The doping component may have been applied to the doped metal catalyst by absorption, adsorption or deposition. The doped metal catalyst may be a mixture composed of at least two metals and/or metal compounds, the catalytically active species being formed only during the hydrogenation, from precursors.
The doping component for the doped metal catalysts may comoprise alkali metals or alkali metal compounds, preferably based on Li, Na, K or Rb, alkaline earth metals or alkaline earth metal compounds, preferably based on Be, Mg, Ca, Sr or Ba, elements from main group 3 and compounds of main group 3, preferably based on B, Al, Ga or In, elements from main group 4 and compounds of main group 4, preferably based on C, Si, Ge, Sn or Pb, elements from main group 5 and compounds of main group 5, preferably based on N, P, As or Sb, elements from main group 6 and compounds of main group 6, preferably based on O, S, Se or Te, elements from main group 7 and compounds of main group 7, preferably based on F, Cl, Br or I, transition group elements and compounds of transition group elements, preferably based on Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn or Cd, elements of the lanthanoid group and compounds of the lanthanoids, preferably based on lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, ytterbium or lutetium.
The doping component may be free from ruthenium oxide, from nickel oxide and from palladium oxide. The doping component may be different from the catalyst support material. A preferred doping component is a hydride, oxide, halide, for example fluoride, chloride, bromide or iodide, sulphide or nitride.
The doped metal catalysts may preferably comprise as substance hydrides, oxides, halides, sulphides and/or nitrides of Fe, Ni, Ru, Rh, Pd, Os or Ir.
The doped metal catalysts may preferably comprise as doping component hydrides, oxides, halides, sulphides and/or nitrides of Fe, Ni, Ru, Rh, Pd, Os or Ir. The doping component may preferably comprise oxides, for example nickel oxide, iron oxide, ruthenium oxide, rhodium oxide, osmium oxide, iridium oxide and palladium oxide. It may preferably comprise sulphides, for example nickel sulphide, iron sulphide, ruthenium sulphide, rhodium sulphide, osmium sulphide, iridium sulphide and palladium sulphide.
The doped metal catalysts may be porous skeletal or activated metal catalysts of the Raney type which have been doped with transition metals and/or transition metal compounds, molybdenum for example. The doped metal catalysts may preferably be activated nickel metal catalysts of the Raney type that have been doped with transition metals and/or transition metal compounds, molybdenum for example.
Examples of doped metal catalysts which can be used are the catalysts BK 111 W (activated, nickel-based metal catalyst doped with <5% by weight molybdenum) and BK 113 W (activiated, nickel-based metal catalyst doped with <5% by weight molybdenum) from Degussa AG.
The weight fraction of the doping component (present in elemental form or as a chemical compound), based on the weight of the doped metal catalyst, can be 0.00001% to 80%, preferably 0.0001% to 50%, more preferably 0.001% to 15%, very preferably 0.01% to 7.5%, by weight.
The doped component may form a physical mixture with the substance of the doped metal catalyst and/or its precursors and/or the catalyst support material. The doping component may form a chemical compound with the substance of the doped metal catalyst and/or its precursors and/or the catalyst support material.
The doping component may form an alloy with the substance of the doped metal catalyst and/or its precursors. It may also form mixed crystals with the substance of the doped metal catalyst and/or its precursors.
The doped metal catalyst may be composed of finely divided, unsupported, activated metals and/or metal compounds. It may have been applied to one of the known and customary catalyst support materials, such as diatomaceous earth (kieselguhr), carbon, silica, activated carbons, alumina or aluminosilicate.
The substance of the doped metal catalyst and also the doping component may be applied together, separately or successively to one of the known and customary catalyst support materials, such as diatomaceous earth (kieselguhr), carbon, silica, activated carbons, alumina or aluminosilicate.
The doped metal catalysts may be used in solid form, in suspension or embedded in waxes or oils for the reaction. The catalyst concentration, based on the molar amount of the substance of the doped metal catalyst, may be 0.0001 to 1 mmol per g of bis(alkoxysilylorganyl) polysulphide.
For nickel and iron the concentration, based on the amount of substance of the doped metal catalyst, may be preferably from 0.001 to 1 mmol, more preferably 0.01 to 1 mmol, very preferably 0.05 to 0.5 mmol, per g of bis(alkoxysilylorganyl) polysulphide.
For ruthenium, rhodium, osmium or iridium the concentration, based on the amount of substance of the doped metal catalyst, may be preferably from 0.0001 to 1 mmol, more preferably 0.005 to 0.5 mmol, very preferably 0.005 to 0.1 mmol, per g of bis(alkoxysilylorganyl) polysulphide.
For palladium the concentration, based on the amount of substance of the doped metal catalyst, may be preferably from 0.0001 to 1 mmol, more preferably 0.005 to 1 mmol, very preferably 0.01 to 0.5 mmol, per g of bis(alkoxysilylorganyl) polysulphide.
Parameters serving for comparison of the rate of hydrogenolysis at a given temperature T and a constant pressure p may be the weight conversion, which can be expressed quantitatively by the relationship “product in g” per “mmol of substance of the doped metal catalyst” per “minute”. As further parameters for comparing the rate of the hydrogenolysis at a given temperature T and a constant pressure p it is possible to employ the molar conversion, which can be expressed quantitatively by the relationship “product in mmol” per “mmol of substance of the doped metal catalyst” per “minute”.
If it is possible to raise the conversion at lower temperatures and/or lower pressures, this constitutes a substantial improvement in terms of ecology, energy and economics. The weight conversion can be 0.001 to 10 g of mercaptoorganyl(alkoxysilane) per mmol of doped metal or metal compound per minute. The molar conversion can be 0.001 to 50 mmol of mercaptoorganyl(alkoxysilane) per mmol of doped metal per minute.
For the substance of the doped metal catalyst as nickel, ruthenium, rhodium, iridium or palladium, the weight conversion can be preferably 0.001 to 10 g, more preferably 0.01 to 10 g, very preferably 0.1 to 10 g of mercapto-organyl(alkoxysilane) per mmol of doped metal per minute. For the substance of the doped metal catalyst as nickel, ruthenium, rhodium, iridium or palladium the molar conversion can be preferably 0.001 to 50 mmol, preferably 0.01 to 40 mmol, more preferably 0.05 to 30 mmol, very preferably 0.1 to 20 mmol of mercaptoorganyl(alkoxysilane) per mmol of doped metal per minute.
Using the process of the invention it is possible to convert more than 80%, preferably more than 83%, more preferably more than 86%, very preferably more than 90%, by weight, of the bis(alkoxysilylorganyl) polysulphides employed into a mercaptoorganyl(alkoxysilane). With the process of the invention the relative fraction (mol %) of the bis(alkoxysilylorganyl) monosulphide present in the bis(alkoxysilylorganyl) polysulphides employed may remain constant. The relative fraction of the bis(alkoxysilyl-organyl) monosulphide present in the reactant may be <10%, preferably <8%, more preferably <6%, very preferably <4%, by weight.
The process of the invention may be a batch process or a continuous process. In the case of the batch process it may be a slurry process or suspension process, in stirred autoclaves or Buss reactors, for example.
In the case of continuous processes the process may be a slurry process with continuous supply of gas and liquid. In the case of the continuous process it is possible to employ known reactors for gas/liquid/solid reactions. Typical representatives of fixed-bed reactors may be the trickle-bed reactor and liquid-filled reactor; for suspension reactors, the stirred tank, the bubble column and the fluidized bed.
The process of the invention has the advantage that higher conversions are obtained when using doped catalysts than when employing undoped catalysts. In comparison to the prior art (U.S. Pat. No. 6,433,206) it is possible using doped catalysts to obtain higher conversions on a metal-specific or substrate-specific basis, at milder temperatures and/or pressures. The higher conversion not only considerably improves the space-time yield but also lowers the specific energy consumption for the preparation of mercapto-organyl(alkoxysilanes) by reductive cleavage with H2 from bis(alkoxysilylorganyl) polysulphides. The lower energy consumption and milder reaction conditions impose less stress on the plant, resulting in, among other things, reduced wear and maintenance expenditure. A lower energy consumption in the preparation of mercaptoorganyl(alkoxysilanes) improves the energy balance of the process and imposes less of a burden on the environment. The complexity of technical plant generally decreases as process temperatures and process pressures become lower.
EXAMPLES
Table 1 lists examples from U.S. Pat. No. 6,433,206. The polysulphanesilane used is an unspecified disulphanesilane mixture containing primarily bis(3-triethoxysilylpropyl) disulphide. No formation of by-products is described. Product analysis takes place by gas chromatography methods or techniques.
Table 2 describes, as comparative example 1, the use of an undoped palladium catalyst at 155° C. and 51 bar. In order to achieve effective comparability of the results the percentages by weight in the comparative examples in tables 1 and 2 are corrected for the alcohol fractions of the product solution (example: a 50% strength product solution of alcohol and silane contains 25% by weight mercaptosilane and 25% by weight disulphanesilane. In other words, the silane constituents of the product are 50% by weight mercaptosilane and 50% by weight disulphanesilane.).
The stated weight percentages of the silane constituents in Tables 3 and 4 are likewise corrected for the alcohol fraction of the solutions.







TABLE 1





Comparative examples as per U.S. Pat. No. 6,433,206































Molar











amount of








Amount of
metal








metal
employed,







Amount of
based on
based on
Polysulphane-



Temperature
Pressure
Pressure
Catalyst
catalyst
catalyst
catalyst
silane
EtOH


No.
° C.
psig
bar
type
g
g
mmol
g
g





19
190
300
51
55% Ni/silica
5
2.75
46.9
256
251






(G-49B)


46.9
256
251


22
190
300
51
55% Ni/silica
5
2.75
46.9
498
53






(G-49B)


46.9
498
53









46.9
498
53


 5
190
1400
235.2
5% Pd/C
6
0.3
2.82
359
324


 8
190
1400
235.2
10% Pd/C
6
0.6
5.64
255
254


























Ratio of










silane










formed to










amount of










catalyst










metal per










minute










(weight




EtOH
Time
SH
S1
S2
Polysulphide
conversion)



No.
% by wt.
min
% by wt.
% by wt.
% by wt.
% by wt.
g/mmol/min







19
49.5
60
24.9
4.33
16.5
1.5
0.045




49.5
120
44.5
5.5
0
0
0.040



22
9.6
60
18.2
7.6
51.4
5.7
0.036




9.6
120
35.3
7.85
39.1
2.5
0.035




9.6
180
55.9
8
19.4
0
0.037



 5
47.44
60
14.1
7.8
61.8
7.8
0.30



 8
49.90
60
14.2
7.2
54.9
7.8
0.11

















TABLE 2







Comparative example 1



































Ratio of
















silane
















formed to
















amount of
















catalyst






Amount
Amount








metal per






of metal
of metal








minute


Temper-
Pres-

Mass of
based on
based on
Polysulphane-

EtOH

SH
S2
S3
Polysulphide
(weight


ature
sure
Catalyst
catalyst
catalyst
catalyst
silane
EtOH
% by
Time
% by
% by
% by
% by
conversion)


° C.
bar
type
mg
mg
mmol
g
g
wt.
min
wt.
wt.
wt.
wt.
g/mmol/min





155
51
E105Y/
20.2
1.01
0.009
0.28
4.52
94
211
95.8
4.2
0
0
0.136




W 5%




Pd









Tables 3 and 4 summarize the inventive examples based on a disulphanesilane (Si 266=commercial product from Degussa AG=[bis(triethoxysilylpropyl)disulphide]). In an apparatus consisting of 8 parallel, oilbath-heated autoclaves with a reactor volume of 20 ml each and equipped with anchor-shaped magnetic stirrers which rotate at 1300 rpm on a fixed shaft located in the centre of the reactor, Si 266 is catalytically hydrogenated in accordance with the conditions and relationships shown in tables 3 and 4.
The reaction is ended after the stated times. The product composition is determined by means of 1H NMR and the conversion is determined from the product composition.
The average chain length of the polysulphane mixture, determined by HPLC, is 2.14 (only the HPLC-determined mean value of S2-S14 is taken into account). The average molecular weight which results for Si 266 is 460 g/mol.
The product composition columns in Tables 3 and 4 take account only of the following components: 3-mercaptopropyl(triethoxysilane), bis(triethoxysilylpropyl) disulphide, bis(triethoxysilylpropyl)trisulphide and bis(triethoxysilylpropyl) polysulphide (Sx mit x>3).
Bis(triethoxysilylpropyl) monosulphide and 3-chloro-propyl(triethoxysilane) are disregarded.

















TABLE 3












Amount
Amount











of metal
of metal







based
based






Mass of
on
on
Polysulphane-



Temperature
Pressure
Catalyst
catalyst
catalyst
catalyst
silane
EtOH
EtOH
Time


No.
° C.
bar
type
mg
mg
mmol
g
g
wt. %
min





1
167
50
T-8027
50.20
26.10
0.44
5.00
1.30
20.6
139.00


2
159
50
T-8027
30.60
15.91
0.27
5.00
1.30
20.6
132.00


3
161
50
T-8027
50.20
26.10
0.44
4.00
2.50
38.5
132.00


4
167
50
T-8027
31.00
16.12
0.27
4.00
2.50
38.5
122.00























Ratio of silane
Ratio of silane








formed to
formed to








amount of
amount of








catalyst metal
catalyst metal








per minute
per minute








(weight
(molar




SH
S2
S3
Polysulphide
conversion)
conversion)



No.
wt. %
wt. %
wt. %
wt. %
g/mmol/min
mmol/mmol/min







1
75.60
24.40
0.00
0.00
0.061
0.257



2
38.90
58.60
2.50
0.00
0.054
0.228



3
82.70
17.30
0.00
0.00
0.056
0.237



4
50.20
49.80
0.00
0.00
0.060
0.252



























TABLE 4












Amount












of metal
Amount







based
of metal






Mass of
on
based on
Polysulphane-



Temperature
Pressure
Catalyst
catalyst
catalyst
catalyst
silane
EtOH
EtOH
Time


No.
° C.
bar
type
mg
mg
mmol
g
g
wt. %
min





5
152
50
E 105
20.1
1.005
0.009
0.28
4.52
0.94
137





XRS/W





5% Pd; S





doped


6
126
50
CE 101
20
1
0.009
0.28
4.52
0.94
55





XR/W





5% Pd + 1%





Sn


7
154
50
CE 105
20.8
1.04
0.010
0.28
4.52
0.94
80





XR/W





5% Pd + 0.5%





Mo























Ratio of silane
Ratio of








formed to
silane formed








amount of
to amount of








catalyst metal
catalyst metal








per minute
per minute








(weight
(molar




SH
S2
S3
Polysulphide
conversion)
conversion)



No.
wt. %
wt. %
wt. %
wt. %
g/mmol/min
mmol/mmol/min







5
100
0
0
0
0.220
0.923



6
100
0
0
0
0.550
2.312



7
96
4
0
0
0.349
1.467










The abbreviations in the tables have the following meanings:

    SH=3-mercaptopropyl(triethoxysilane),
    S2=bis(triethoxysilylpropyl) disulphide,
    S3=bis(triethoxysilylpropyl) trisulphide,
    polysulphide=bis(triethoxysilylpropyl) polysulphide (Sx with x>3).


The catalysts with the abbreviated designations:

    
    
        E 105 Y/W 5% Pd
        E 105 XRS/W 5% Pd; S doped
        CE 101 XR/W 5% Pd+1% Sn
        CE 105 XR/W 5% Pd+0.5% Mo

are commercial products from Degussa AG which are produced by applying a noble metal component, such as palladium, to a porous support material of high surface area. The catalysts are employed in the form of free-flowing powderous solids. The stated catalysts are supported on activated carbons. The catalysts with the abbreviated designations given below contain the following amounts of active metal:

        E 105 Y/W 5% Pd=5% Pd based on the dry mass of the catalyst;
        E 105 XRS/W 5% Pd=5% Pd based on the dry mass of the catalyst;
        CE 101 XR/W 5% Pd+1% Sn=5% Pd based on the dry mass of the catalyst;
        CE 105 XR/W 5% Pd+0.5% Mo=5% Pd based on the dry mass of the catalyst.
    
    


The catalysts with the abbreviated designations given below contain the following amounts of doping component:

    
    
        E 105 XRS/W 5% Pd=doped with S
        CE 101 XR/W 5% Pd+1% Sn=doped with 1% Sn
        CE 105 XR/W 5% Pd+0.5% Mo=doped with 0.5% Mo.
    
    


The catalysts G-49 B and T 8027 are commercial products from Süd-Chemie AG. The catalyst G-49 B contains 55% nickel and is undoped. The catalyst T 8027 contains 52% nickel and is doped with 2.4% zirconium.
The products are analysed using a DRX 500 NMR instrument from Bruker, in accordance with the operating procedures and rules that are known to the skilled person. The measurement frequencies are 99.35 MHz for 29Si nuclei and 500.13 MHz for 1H nuclei. The reference used is tetramethylsilane (TMS).
Bis(alkoxysilylorganyl) polysulphides and mixtures thereof can be analysed using GC and HPLC (U. Görl, J. Münzenberg, D. Luginsland, A. Müller Kautschuk Gummi Kunststoffe 1999, 52(9), 588, D. Luginsland Kautschuk Gummi Kunststoffe 2000, 53(1-2), 10, M. W. Backer et al., Polymer Preprints 2003, 44(1), 245). From the data set out in Tables 1 to 4 it is clear that the use of doped metal catalysts permits at least equally high conversions under more energy-sparing conditions as compared with the prior art (U.S. Pat. No. 6,433,206).
The doping of palladium with sulphur, tin or molybdenum results in conversions which are higher in some cases under more energy-saving conditions or similar conditions.
The doping of nickel with zirconium leads, for example, to an increase in conversions under more energy-sparing conditions as compared with the prior art (U.S. Pat. No. 6,433,206).
All references cited herein are fully incorporated by reference. Having now fully described the invention, it will be understood by those of skill in the art that the invention may be practiced within a wide and equivalent range of conditions, parameters and the like, without affecting the spirit or scope of the invention or any embodiment thereof.

## Claims

1. A process for preparing mercaptoorganyl(alkoxysilanes) comprising: hydrogenating bis(alkoxysilylorganyl) polysulphides with hydrogen in the presence of at least one alcohol and a doped metal catalyst, wherein the doped metal catalyst comprises at least one substance selected from the group consisting of: iron, iron compound, osmium, osmium compound, ruthenium, ruthenium compound, and at least one doping component, wherein said doping component comprises 0.001% to 15% by weight of said doped metal catalyst.

2. The process for preparing mercaptoorganyl(alkoxysilanes) of claim 1, wherein the weight conversion is 0.00 1 to 10 g of mercaptoorganyl(alkoxysilane) per mmol of substance of the doped metal catalyst per minute.

3. The process for preparing mercaptoorganyl(alkoxysilanes) of claim 1, wherein the molar conversion is 0.001 to 50 mmol of mercaptoorganyl(alkoxysilane) per mmol of substance of the doped metal catalyst per minute.

4. The process for preparing mercaptoorganyl(alkoxysilanes) of claim 1, wherein the hydrogenation is carried out at a temperature of between 100 and 175° C. and under a hydrogen pressure of 5 to 55 bar, and wherein said doping component comprises 0.01%-7.5% by weight of said doped metal catalyst.

5. The process of claim 1, wherein said doping component is sulphur, tin molybdenum or zirconium.

6. The process of claim 1, wherein said doped metal catalyst is formed by the absorption, adsorption or deposition of said doping component.

7. The process for preparing mercaptoorganyl(alkoxysilanes) of claim 1, wherein said mercaptoorganyl(alkoxysilanes) are compounds of the general formula (II):


W-A-SH  (II)


wherein:
W is SiY1Y2Y3 or Si(OCH2—CH2—)3N and Y1, Y2, Y3 each independently of one another may be hydroxyl (—OH), a linear, branched or cyclic hydrocarbon chain having 1-18 carbon atoms (C1-C18), a linear or branched alkyl acid group (CaH2a+1)—C(═O)O—with a=1-25, a linear or branched alkenyl acid group (CbH2b−1)—C(═O)O— with b=2-25, a linear or branched substituted alkyl or alkenyl acid group, an unsubstituted, halogen-substituted or alkyl-substituted cycloalkane radical having 5-12 carbon atoms, benzyl radical, a halogen-substituted or alkyl-substituted phenyl radical, a linear or branched alkoxy group, a cycloallcoxy group having 5-12 carbon atoms, a halogen-substituted or alkyl-substituted phenoxy or benzyloxy group, an alkyl ether group O—(CRI2—CRI2)—O-Alk or alkyl polyether group O—(CRI2—CRI2O)y-Alk, with y=2-25 and wherein RI independently at each occurrence is H or an alkyl group, Alk being a linear or branched, saturated or unsaturated alkyl chain having 1-30 carbon atoms (C1-C30), and
A is a linear or branched, saturated or unsaturated aliphatic, aromatic or mixedly aliphatic/aromatic divalent C1-C30 hydrocarbon chain.

8. The process for preparing a mercaptoorganyl(alkoxysilane) of claim 7, wherein said mercaptoorganyl(alkoxysilane) of formula (II) is selected from the group consisting of:
3-mercaptopropyl(trimethoxysilane), 3-mercaptopropyl(dimethoxyhydroxysilane), 3-mercaptopropyl(triethoxysilane), 3-mercaptopropyl(diethoxyhydroxysilane), 3-mercaptopropyl(diethoxymethoxysilane), 3-mercaptopropyl(tripropoxysilane), 3-mercaptopropyl(dipropoxymethoxysilane), 3-mercaptopropyl(dipropoxyhydroxysilane), 3-mercaptopropyl(tridodecanoxysilane), 3-mercaptopropyl(didodecanoxyhydroxysilane), 3-mercaptopropyl(tritetradecanoxysilane), 3-mercaptopropyl(trihexadecanoxysilane), 3-mercaptopropyl(trioctadecanoxysilane), 3-mercaptopropyl(didodecanoxy)tetradecanoxysilane, 3-mercaptopropyl(dodecanoxy)tetradecanoxy(hexadecanoxy)silane, 3-mercaptopropyl(dimethoxymethylsilane), 3-mercaptopropyl(methoxymethylhydroxysilane), 3-mercaptopropyl(methoxydimethylsilane), 3-mercaptopropyl(hydroxydimethylsilane), 3-mercaptopropyl(diethoxymethylsilane), 3-mercaptopropyl(ethoxyhydroxymethylsilane), 3-mercaptopropyl(ethoxydimethylsilane), 3-mercaptopropyl(dipropoxymethylsilane), 3-mercaptopropyl(propoxymethylhydroxysilane), 3-mercaptopropyl(propoxydimethylsilane), 3-mercaptopropyl(diisopropoxymethylsilane), 3-mercaptopropyl(isopropoxydimethylsilane), 3-mercaptopropyl(dibutoxymethylsilane), 3-mercaptopropyl(butoxydimethylsilane), 3-mercaptopropyl(disiobutoxymethylsilane), 3-mercaptopropyl(siobutoxymethylhydroxysilane), 3-mercaptopropyl(isobutoxydimethylsilane), 3-mercaptopropyl(didodecanoxymethylsilane), 3-mercaptopropyl(dodecanoxydimethylsilane), 3-mercaptopropyl(ditetradecanoxymethylsilane), 3-mercaptopropyl(tetradecanoxymethylhydroxysilane), 3-mercaptopropyl(tetradecanoxydimethylsilane), 2-mercaptoethyl(trimethoxysilane), 2-mercaptoethyl(triethoxysilane), 2-mercaptoethyl(diethoxymethoxysilane), 2-mercaptoethyl(tripropoxysilane), 2-mercaptoethyl(dipropoxymethoxysilane), 2-mercaptoethyl(tridodecanoxysilane), 2-mercaptoethyl(tritetradecanoxysilane), 2-mercaptoethyl(trihexadecanoxysilane), 2-mercaptoethyl(trioctadecanoxysilane), 2-mercaptoethyl(didodecanoxy)tetradecanoxysilan, 2-mercaptoethyl(dodecanoxy)tetradecanoxy(hexadecanoxy)silane, 2-mercaptoethyl(dimethoxymethylsilane), 2-mercaptoethyl(methoxymethylhydroxysilane), 2-mercaptoethyl(methoxydimethylsilane), 2-mercaptoethyl(diethoxymethylsilane), 2-mercaptoethyl(ethoxydimethylsilane), 2-mercaptoethyl(hydroxydimethylsilane), 1-mercaptomethyl(trimethoxysilane), 1-mercaptomethyl(triethoxysilane), 1-mercaptomethyl(diethoxymethoxysilane), 1-mercaptomethyl(diethoxyhydroxysilane), 1-mercaptomethyl(dipropoxymethoxysilane), 1-mercaptomethyl(tripropoxysilane), 1-mercaptomethyl(trimethoxysilane), 1-mercaptomethyl(dimethoxymethylsilane), 1-mercaptomethyl(methoxydimethylsilane), 1-mercaptomethyl(diethoxymethylsilane), 1-mercaptomethyl(ethoxymethylhydroxysilane), 1-mercaptomethyl(ethoxydimethylsilane), 3-mercaptobutyl(trimethoxysilane), 3-mercaptobutyl(triethoxysilane), 3-mercaptobutyl(diethoxymethoxysilane), 3-mercaptobutyl(tripropoxysilane), 3-mercaptobutyl(dipropoxymethoxysilane), 3-mercaptobutyl(dimethoxymethylsilane), 3-mercaptobutyl(diethoxymethylsilane), 3-mercaptobutyl(dimethylmethoxysilane), 3-mercaptobutyl(dimethylethoxysilane), 3-mercaptobutyl(dimethylhydroxysilane), 3-mercaptobutyl(tridodecanoxysilane), 3-mercaptobutyl(tritetradecanoxysilane), 3-mercaptobutyl(trihexadecanoxysilane), 3-mercaptobutyl(didodecanoxy)tetradecanoxysilan, 3-mercaptobutyl(dodecanoxy)tetradecanoxy(hexadecanoxy)silane, 3-mercapto-2-methyl-propyl(trimethoxysilane), 3-mercapto-2-methyl-propyl(triethoxysilane), 3-mercapto-2-methyl-propyl(diethoxymethoxysilane), 3-mercapto-2-methyl-propyl(tripropoxysilane), 3-mercapto-2-methyl-propyl(dipropoxymethoxysilane), 3-mercapto-2-methyl-propyl(tridodecanoxysilane), 3-mercapto-2-methyl-propyl(tritetradecanoxysilane), 3-mercapto-2-methyl-propyl(trihexadecanoxysilane), 3-mercapto-2-methyl-propyl(trioctadecanoxysilane), 3-mercapto-2-methyl-propyl(didodecanoxy)tetradecanoxysilane, 3-mercapto-2-methyl-propyl(dodecanoxy)tetradecanoxy(hexadecanoxy)silane, 3-mercapto-2-methyl-propyl(dimethoxymethylsilane), 3-mercapto-2-methyl-propyl(methoxydimethylsilane), 3-mercapto-2-methyl-propyl(diethoxymethylsilane), 3-mercapto-2-methyl-propyl(ethoxydimethylsilane), 3-mercapto-2-methyl-propyl(hydroxydimethylsilane), 3-mercapto-2-methyl-propyl(dipropoxymethylsilane), 3-mercapto-2-methyl-propyl(propoxydimethylsilane), 3-mercapto-2-methyl-propyl(diisopropoxymethylsilane), 3-mercapto-2-methyl-propyl(isopropoxydimethylsilane), 3-mercapto-2-methyl-propyl(dibutoxymethylsilane), 3-mercapto-2-methyl-propyl(butoxydimethylsilane), 3-mercapto-2-methyl-propyl(diisobutoxymethylsilane), 3-mercapto-2-methyl-propyl(isobutoxydimethylsilane), 3-mercapto-2-methyl-propyl(didodecanoxymethylsilane), 3-mercapto-2-methyl-propyl(dodecanoxydimethylsilane), 3-mercapto-2-methyl-propyl(ditetradecanoxymethylsilane), 3-mercapto-2-methyl-propyl(tetradecanoxydimethylsilane), [(C9H19O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6]3Si(CH2)3SH, and HS—CH2—CH2—CH2—Si(OCH2—CH2—)3N.

9. The process for preparing mercaptoorganyl(alkoxysilanes) of claim 8, wherein the hydrogenation is carried out at a temperature of between 100 and 175° C. and under a hydrogen pressure of 5 to 55 bar.

10. The process for preparing mercaptoorganyl(alkoxysilanes) of claim 9, wherein said process is carried out in a reaction mixture comprising an additive selected from the group consisting of: a titanium alkoxylate; an amine; water; and an organic or inorganic acid or base.

11. A process for preparing mercaptoorganyl(alkoxysilanes) comprising: hydrogenating bis(alkoxysilylorganyl) polysulphides with hydrogen in the presence of at least one alcohol and a doped metal catalyst, wherein the doped metal catalyst comprises at least one substance selected from the group consisting of: nickel, nickel compound, palladium, palladium compound, rhodium, rhodium compound, iridium and iridium compound, and at least one doping component.

12. The process of claim 11, wherein said doping component is sulphur, tin molybdenum or zirconium.

13. The process of claim 12, wherein said doped metal catalyst comprises palladium or a palladium compound and one or more doping components selected from the group consisting of: sulphur, tin and molybdenum.

14. The process of claim 12, wherein said doped metal catalyst comprises nickel or a nickel compound and zirconium.

15. The process of claim 11, wherein said doping component comprises 0.01%-7.5% by weight of said doped metal catalyst.

16. The process of claim 11, wherein said doped metal catalyst is formed by the absorption, adsorption or deposition of said doping component.

17. The process for preparing mercaptoorganyl(alkoxysilanes) of claim 11, wherein said mercaptoorganyl(alkoxysilanes) are compounds of the general formula (II):


W-A-SH   (II)


wherein:
W is SiY1Y2Y3 or Si(OCH2—CH2—)3N and Y1, Y2, Y3 each independently of one another may be hydroxyl (—OH), a linear, branched or cyclic hydrocarbon chain having 1-18 carbon atoms (C1-C18), a linear or branched alkyl acid group (CaH2a+1)—C(═O )O— with a=1-25, a linear or branched alkenyl acid group (CbH2b−1)—C(═O)O— with b=2-25, a linear or branched substituted alkyl or alkenyl acid group, an unsubstituted, halogen-substituted or alkyl-substituted cycloalkane radical having 5-12 carbon atoms, benzyl radical, a halogen-substituted or alkyl-substituted phenyl radical, a linear or branched alkoxy group, a cycloalkoxy group having 5-12 carbon atoms, a halogen-substituted or alkyl-substituted phenoxy or benzyloxy group, an alkyl ether group O—(CRI2—CRI2)—O-Alk or alkyl polyether group O—(CRI2—CRI2O)y-Alk, with y=2-25 and wherein RI independently at each occurrence is H or an alkyl group, Alk being a linear or branched, saturated or unsaturated ailcyl chain having 1-30 carbon atoms (C1-C30), and
A is a linear or branched, saturated or unsaturated aliphatic, aromatic or mixedly aliphatic/aromatic divalent C1-C30 hydrocarbon chain.

18. The process for preparing a mercaptoorganyl(alkoxy-silane) of claim 17, wherein said mercaptoorganyl(alkoxy-silane) of formula (II) is selected from the group consisting of:
3-mercaptopropyl(trimethoxysilane), 3-mercaptopropyl(dimethoxyhydroxysilane), 3-mercaptopropyl(triethoxysilane), 3-mercaptopropyl(diethoxyhydroxysilane), 3-mercaptopropyl(diethoxymethoxysilane), 3-mercaptopropyl(tripropoxysilane), 3-mercaptopropyl(dipropoxymethoxysilane), 3-mercaptopropyl(dipropoxyhydroxysilane), 3-mercaptopropyl(tridodecanoxysilane), 3-mercaptopropyl(didodecanoxyhydroxysilane), 3-mercaptopropyl(tritetradecanoxysilane), 3-mercaptopropyl(trihexadecanoxysilane), 3-mercaptopropyl(trioctadecanoxysilane), 3-mercaptopropyl(didodecanoxy)tetradecanoxysilane, 3-mercaptopropyl(dodecanoxy)tetradecanoxy(hexadecanoxy)silane, 3-mercaptopropyl(dimethoxymethylsilane), 3-mercaptopropyl(methoxymethylhydroxysilane), 3-mercaptopropyl(methoxydimethylsilane), 3-mercaptopropyl(hydroxydimethylsilane), 3-mercaptopropyl(diethoxymethylsilane), 3-mercaptopropyl(ethoxyhydroxymethylsilane), 3-mercaptopropyl(ethoxydimethylsilane), 3-mercaptopropyl(dipropoxymethylsilane), 3-mercaptopropyl(propoxymethylhydroxysilane), 3-mercaptopropyl(propoxydimethylsilane), 3-mercaptopropyl(diisopropoxymethylsilane), 3-mercaptopropyl(isopropoxydimethylsilane), 3-mercaptopropyl(dibutoxymethylsilane), 3-mercaptopropyl(butoxydimethylsilane), 3-mercaptopropyl(disiobutoxymethylsilane), 3-mercaptopropyl(siobutoxymethylhydroxysilane), 3-mercaptopropyl(isobutoxydimethylsilane), 3-mercaptopropyl(didodecanoxymethylsilane), 3-mercaptopropyl(dodecanoxydimethylsilane), 3-mercaptopropyl(ditetradecanoxymethylsilane), 3-mercaptopropyl(tetradecanoxymethylhydroxysilane), 3-mercaptopropyl(tetradecanoxydimethylsilane), 2-mercaptoethyl(trimethoxysilane), 2-mercaptoethyl(triethoxysilane), 2-mercaptoethyl(diethoxymethoxysilane), 2-mercaptoethyl(tripropoxysilane), 2-mercaptoethyl(dipropoxymethoxysilane), 2-mercaptoethyl(tridodecanoxysilane), 2-mercaptoethyl(tritetradecanoxysilane), 2-mercaptoethyl(trihexadecanoxysilane), 2-mercaptoethyl(trioctadecanoxysilane), 2-mercaptoethyl(didodecanoxy)tetradecanoxysilan, 2-mercaptoethyl(dodecanoxy)tetradecanoxy(hexadecanoxy)silane, 2-mercaptoethyl(dimethoxymethylsilane), 2-mercaptoethyl(methoxymethylhydroxysilane), 2-mercaptoethyl(methoxydimethylsilane), 2-mercaptoethyl(diethoxymethylsilane), 2-mercaptoethyl(ethoxydimethylsilane), 2-mercaptoethyl(hydroxydimethylsilane), 1-mercaptomethyl(trimethoxysilane), 1-mercaptomethyl(triethoxysilane), 1-mercaptomethyl(diethoxymethoxysilane), 1-mercaptomethyl(diethoxyhydroxysilane), 1-mercaptomethyl(dipropoxymethoxysilane), 1-mercaptomethyl(tripropoxysilane), 1-mercaptomethyl(trimethoxysilane), 1-mercaptomethyl(dimethoxymethylsilane), 1-mercaptomethyl(methoxydimethylsilane), 1-mercaptomethyl(diethoxymethylsilane), 1-mercaptomethyl(ethoxymethylhydroxysilane), 1-mercaptomethyl(ethoxydimethylsilane), 3-mercaptobutyl(trimethoxysilane), 3-mercaptobutyl(triethoxysilane), 3-mercaptobutyl(diethoxymethoxysilane), 3-mercaptobutyl(tripropoxysilane), 3-mercaptobutyl(dipropoxymethoxysilane), 3-mercaptobutyl(dimethoxymethylsilane), 3-mercaptobutyl(diethoxymethylsilane), 3-mercaptobutyl(dimethylmethoxysilane), 3-mercaptobutyl(dimethylethoxysilane), 3-mercaptobutyl(dimethylhydroxysilane), 3-mercaptobutyl(tridodecanoxysilane), 3-mercaptobutyl(tritetradecanoxysilane), 3-mercaptobutyl(trihexadecanoxysilane), 3-mercaptobutyl(didodecanoxy)tetradecanoxysilan, 3-mercaptobutyl(dodecanoxy)tetradecanoxy(hexadecanoxy)silane, 3-mercapto-2-methyl-propyl(trimethoxysilane), 3-mercapto-2-methyl-propyl(triethoxysilane), 3-mercapto-2-methyl-propyl(diethoxymethoxysilane), 3-mercapto-2-methyl-propyl(tripropoxysilane), 3-mercapto-2-methyl-propyl(dipropoxymethoxysilane), 3-mercapto-2-methyl-propyl(tridodecanoxysilane), 3-mercapto-2-methyl-propyl(tritetradecanoxysilane), 3-mercapto-2-methyl-propyl(trihexadecanoxysilane), 3-mercapto-2-methyl-propyl(trioctadecanoxysilane), 3-mercapto-2-methyl-propyl(didodecanoxy)tetradecanoxysilane, 3-mercapto-2-methyl-propyl(dodecanoxy)tetradecanoxy(hexadecanoxy)silane, 3-mercapto-2-methyl-propyl(dimethoxymethylsilane), 3-mercapto-2-methyl-propyl(methoxydimethylsilane), 3-mercapto-2-methyl-propyl(diethoxymethylsilane), 3-mercapto-2-methyl-propyl(ethoxydimethylsilane), 3-mercapto-2-methyl-propyl(hydroxydimethylsilane), 3-mercapto-2-methyl-propyl(dipropoxymethylsilane), 3-mercapto-2-methyl-propyl(propoxydimethylsilane), 3-mercapto-2-methyl-propyl(diisopropoxymethylsilane), 3-mercapto-2-methyl-propyl(isopropoxydimethylsilane), 3-mercapto-2-methyl-propyl(dibutoxymethylsilane), 3-mercapto-2-methyl-propyl(butoxydimethylsilane), 3-mercapto-2-methyl-propyl(diisobutoxymethylsilane), 3-mercapto-2-methyl-propyl(isobutoxydimethylsilane), 3-mercapto-2-methyl-propyl(didodecanoxymethylsilane), 3-mercapto-2-methyl-propyl(dodecanoxydimethylsilane), 3-mercapto-2-methyl-propyl(ditetradecanoxymethylsilane), 3-mercapto-2-methyl-propyl(tetradecanoxydimethylsilane), [(C9H19O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5](MeO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6](MeO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4]2(MeO)Si(CH2)3SH, [(C 14H29O—(CH2—CH2O)5]2(MeO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6]2(MeO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5](EtO)2Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6](EtO)2Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5]2(EtO)Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6]2(EtO)Si(CH2)3SH, [(C9H19O—(CH2—CH2O)2]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)3]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)4]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)5]3Si(CH2)3SH, [(C9H19O—(CH2—CH2O)6]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)2]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)3]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)4]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)5]3Si(CH2)3SH, [(C12H25O—(CH2—CH2O)6]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)2]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)3]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)4]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)5]3Si(CH2)3SH, [(C13H27O—(CH2—CH2O)6]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)2]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)3]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)4]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)5]3Si(CH2)3SH, [(C14H29O—(CH2—CH2O)6]3Si(CH2)3SH, and HS—CH2—CH2—CH2—Si(OCH2—CH2—)3N.

19. The process for preparing mercaptoorganyl(alkoxysilanes) of claim 18, wherein said hydrogenation is carried out at a temperature of between 100 and 175° C.; under a hydrogen pressure of 5 to 55 bar and wherein the amount of doping component, based on the weight of the doped metal catalyst, is 0.01%-7.5% by weight.

20. The process for preparing mercaptoorganyl(alkoxysilanes) of claim 19, wherein said process is carried out in a reaction mixture containing an additive selected from the group consisting of: a titanium alkoxylate; an amine; water; and an organic or inorganic acid or base.