MXPA97001413A - The preparation of organosilicio compounds that contain blue - Google Patents

Abstract

The present invention relates to a process for producing organosilicon compound of the formula (I): Z-Alk-Sn-Alk-Z wherein Z is selected from the group consisting of wherein R 1 is an alkyl group of 1 carbon atoms, cyclohexyl or phenyl, R2 is an alkoxy of 1 to 8 carbon atoms, cycloalkoxy of 5 to 8 carbon atoms, Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and n is an integer from 2 to 8; reacting (A) a compound of the formula Z-Alk-X (II) wherein X is Cl or Br; with (B) an ammonium hydrosulfide or alkali metal hydrosulfide and (C) sulfur, wherein the reaction is conducts in the presence of a phase transfer catalyst and a water phase

Description

THE PREPARATION OF ORGAN COMPOUNDS I L I C 10 CONTAINING SULFUR.

BACKGROUND Sulfur-containing organics compounds are useful as reactive coupling agents between rubber and silica replenishers that provide improved physical properties. They are also useful as adhesion primers for glass substrates, metals and others. U.S. Patent Nos. 3,842,111, 3,873,489 and 3,978,103 describe the preparation of various sulfur-containing organosilicon compounds. These organosilicon compounds are prepared by reacting (1) 2 moles of a compound of the formula Z-Alq-hal where 1 is a chlorine, bromine or iodine; Z is 1 1 R -Si- -Si-R '-Si-R' R¿ R¿ R¿ 1 wherein R 1 is an alkyl of 1 to 4 carbon atoms or phenyl and - p R is alkoxy of 1 to 8 carbon atoms, cilokalkoxy of 5 to 8 carbon atoms or alkylmercapto with 1 to 8 carbon atoms; Al is a divalent aliphatic hydrocarbon or unsaturated hydrocarbon or a cyclic hydrocarbon containing 1 to 18 carbon atoms; with (2) 1 mol of a compound of the formula Me2Sn where Me is ammonium or a metal atom and n is an integer from 2 to 6. Since the two starting materials are liquids, the reaction can occur in the absence of a solvent; however, a volatile inert organic solvent is not only used, but generally preferred. The reaction is carried out with the exclusion of water. The reason for the exclusion of water is to avoid the alkaline hydrolysis reaction of the silyl groups which eventually will lead to insoluble polymeric by-products and total lower yield of the desired product. Representative organic solvents include aliphatic alcohols such as methyl alcohol and ethyl alcohol. At the end of the reaction between the two starting materials, the separated salt is removed by filtration. The filtrate is then freed from the solvent by distillation under vacuum. Unfortunately, this process suffers from many practical problems. Many of these problems are related to the solvent, e.g., ethyl alcohol. Ethyl alcohol has a low initial vaporization point. In addition, it is difficult to obtain and maintain in a water-free (anhydrous) state.

SUMMARY OF THE INVENTION The present invention relates to a process for the production of organosiliconium compounds containing sulfur. The process involves reacting (A) a haloalkylsilane compound with (B) an ammonium hydrosulphide or hydrosulphide hydrosulphide. me_ such alkaline and (C) sulfur.

Detailed Description of the Invention A process for the production of organosilicon compounds of the formula is described: Z-Al k-Sn-Al k-Z (I) where Z is selected from the group consisting of wherein R is an alkyl group of 1 to 4 carbon atoms, cyclohexy lo or phenol; 2 R is alkoxy of 1 to 8 carbon atoms, or cycloalkoxy of 5 to 8 carbon atoms. Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and n is an integer of 2 to 8; which comprises reacting (A) a compound of the formula: Z-Alk-X (II) when X is Cl and Br; with (B) an ammonium hydrosulfide or alkali metal hydro-sulfide and (C) sulfur; wherein the reaction is conducted in the presence of a phase transfer catalyst and an aqueous phase. Examples of sulfur-containing organosulfur compounds can be prepared in accordance with the present invention, include: 3, 3 '-bi-disulfide (trimethoxy if 1 and 1 propyl), 3-sulfur-3-sulfur '-bi s (triethoxy si 1 i 1 prop i lo, octasulfuro of 3,3'-bi s (trietoxi si 1 ípropi lo), tetrasulfuro of 3, 3' -bi s (tr imethoxi si -lilpropilo), tetrasulfuro of, 2'-bis (trietoxi si 1 i leti lo), trisuj furo of 3, 3 '-bi s (trimethoxy si 1 i 1 propi lo), trisulfuro of 3, 3' -bis - (trietoxisi 1 i lpropi lo , 3, 3 '-bi s (tr i butoxy 1 i 1 propylo) hexasulfide disulfide, 3 '-bi s (trimethoxy if 1 i 1 propy), octasulfide of 3,3' -bi s (trimethoxy if 1 proton), tetrasulfide of 3, 3 '-bi s (tr ioct xisi 1 i Ipropi), disulfide of 3, 3 '-bi s (tr i hexoxi si 1 i 1 propi lo), trisulfuro of 3, 3' -bis (tri -2"-et i lhexoxi si 1 i propi lo), tetrasulf 3'3'-bis (tri isooctoxisi 1 ipropi, 3, 3'-bis- (tri-t-butoxisi 1 ipropylo) disulfide, 2, 2'-bi s tetrasulfide (methoxy diet xi) silyl ethyl), 2,2 '-bi s pentasulfide (tripropoxysi 1 i leti lo), 3,3' -bis tetrasulfide (tr iciclonexoxi si 1 i propi lo), trisulfide 3,3 '-bi s (tr iciclopentoxi si 1 ípropi lo), 2,2'-bi s tetrasulfuro (tri-2"-meti lcyclohexoxi si 1 i leti lo), tetrasulfuro of bis (trim toxisi 1 i lmeti lo), tetrasulufor of 3-methoxy ethoxy propoxysilyl 3'-diethoxybutoxy-si-1-propyl, 2,2'-bis (dimethyl-ethoxy-lylethyl) -disulfide, 2,2'-bis trisulphide (dimethy 1-butoxy if 1 -alpha), tetrasulfide of 3, 3'-bis (methyl l-buti letoxisi 1 i-propyl), tetrasulf ro of 3, 3'-bi s (di-t-butylmethyl-1-methyl), 2,2'-bis trisulfide (phen i 1 methyl methoxy si 1 i leti lo), 3, 3'-bi s tetrasulfide (difie nil i sopropoxi si 1 i propi lo), 3, 3 '-bi s disulfide (difen i 1 cycle hexoxy si 1 i 1 propy), 3, 3 '-bi s tetrasulfide (dimethyl 1 ethylmercap tosi 1 i 1 propi lo), 2, 2' -bi s trisulfide (methy1 dimethoxy if 1 i let i) tetrasulfide 2, 2 '-bi s (methy1-ethoxypropoxy si 1 i leti it), tetrasul furo of 3, 3' -bi s (dieti 1 methoxy si 1 i lprop i lo), disulfide of 3,3'-bis (et i 1 di -butoxisi 1 i lpropi lo), disulphide of 3, 3 '-bi s (propi 1 diethoxy si 1 protil), trisulfide of 3,3' -bis (buti 1 dimethoxy si 1 i 1 propyl), tetrasulfuro of 3, 3'-bis (phenyl-1-dimethoxy if 1 and 1 propyl), 3-phenyl-ethoxybutoxy tetrasulfide if 1 i 1 3 '-trimethoxy if 1 i 1 propyl tetrasulfide of 4,4' -bi s (tr imetoxi yes 1 i lbuty lo), 6, 6'-bis (triethoxysi 1 ihexyl) tetrasulfide, 12, 12'-bis (tr ii sopro poxysilyl dodecyl) disulfide, 18,18'-bis tetrasulfide (trimethoxy si1 i loc) tadecyl), tetrasulfide of 18, 18 '-bi s (tr i propoxi si 1 i loctadeceni -lo), tetrasulfuro of 4, 4' -bi s (tr i etoxisi 1 i l-buten-2- i lo), tetra sulfide of 4,4 '-bi s (trimethoxy si 1 i le iclohexi leño), trisulfuro of 5, 5' -bi s (dimetoximeti 1 si 1 i lpenti lo, tetrasulfuro of 3, 3 '-bi s (tri methoxy si 1 i 1 -2-meti 1 propi lo) and disulfide of 3, 3 '-bi s (dimethoxy phenij silyl-2-meti lpropi lo). The preferred sulfur-containing organosilicon compounds which are prepared according to the present invention are the 3, 3 '-bi s polysulfides (trimethoxy or triethoxy silicy propyl). The most preferred compound is 3,3'-bis- (triethoxy si 1 -propylo) disulfide. Therefore, as for formula I, preferably Z is R "-Si-R 'R¿ wherein R is an alkoxy of 2 to 4 carbon atoms, with 2 carbon atoms being particularly preferred; Alk is a divalent hydrocarbon of 2 to 4 carbon atoms with 3 carbon atoms being particularly preferred; and n is an integer from 2 to 6 with 2 being particularly preferred. With respect to the first reagent of the formula II used in the present invention, the representative examples include the halogenated substituted forms (chloro and bromo) of ethyl triethoxy silane, propyl triethoxy silane, butyl triethoxy silane, -pentyl triethoxy silane, hexyl triethoxy silane, heptyl triethoxy sj_ tin, actyl triethoxy silane, nonyl triethoxy silane, decyl triethoxy silane, undecyl triethoxy silane, dodecyl triethoxy silane, tri-decyl triethoxy silane, tetradecyl triethoxy silane and penta triethoxy silane to name a few. The second reagent in the present process is an ammonium hydrosulfide or alkali metal hydrosulfide. Representative metals include potassium, sodium, rubidium or cesium. Preferably, the alkali metal is sodium. Specific examples of these compounds include C HS, KHS, NaHS, NaHS * 2H? 0, NaHS'3H20 and NH2Hx By varying the orlar ratio of the compound of formula II to hydrosulfide, the resulting reaction product can be controlled. Generally speaking, the molar ratio of the compound of formula II to hydrosulfide varies from 1: 1 to more than 1: 5. If a higher concentration of a disulfide product is desired, a molar ratio of 1: 3 or greater is used. If a higher concentration of a tetrasulfide product is desired, a lower molar in excess of the hydrosulfide is used. The third compound used in the present invention is sulfur, Sg. It is believed that sulfur can react first - with the hydrosulfide to form an intermediate with sut reaction > sequential of the intermediary with haloalqui 1 s i lño. It is believed that the higher the molar ratio of sulfur to hydrosulfide, the greater the tendency towards product formation when n is a higher interest. By varying the molar ratio of sulfur to hydrosulfide, the resulting reaction product can be controlled. Generally speaking, the molar ratio of sulfur to hydrosulfur varies from 4: 1 to 1:28. If a higher concentration-of a disulfide product is desired, a molar excess of hydrosulfide, such as a molar ratio of 1:16, is used. If a higher concentration of a tetrasulfide product is desired, a higher concentration of sulfur is used; for example, 1: 1 to 4: 1. The reaction is conducted in the presence of a phase transfer catalyst. Representative phase transfer catalysts may have a quaternary onium cation of the following structural formulas (III), (IV) or (V): R ' l + (IV, 9 11 (R12) (CH2) and - (R *) (V) 13 13 ? C. f. wherein A represents nitrogen, phosphorus or arsenic; R, R, RR, which may be the same or different, are each a straight or branched chain alkyl radical containing from 1 to 16 carbon atoms, optionally substituted by a n -yl, hydroxyl, halo, nitro, alkoxy or to coxicarbon i lo; a straight or branched chain alkenyl radical containing from 2 to -12 carbon atoms, preferably from 4 to 8 carbon atoms and more preferably an alkenyl radical derived from the conjugated diene starting material; an aryl radical containing from 6 to 10 carbon atoms, optionally substituted by one or more alkyl substituents containing from 1 to 4 carbon atoms or alkoxy, alkoxycarbonyl or halo substituents; and with the proviso that any two of the radicals R to R can form together a single straight or branched chain alkylene, alkenylene or alkadiene radical containing from 3 to 6 carbon atoms. 11 carbon, R, R, R, R, which may also be the same or different, are each a straight chain or branched alkyl radical containing from 1 to 4 carbon atoms; with the proviso that R and the radicals R can together form an ak-chiral radical containing from 3 to 6 carbon atoms; and with the additional proviso that the radicals R and R or R and R can - together form an alkylene, alkenylene or cadherium radical - containing 4 carbon atoms, and together with the nitroge atom 12, which comprises a 5-membered nitrogen heterocycle; R is a straight or branched chain alkyl radical containing 13 of 1 to 4 carbon atoms, or a phenyl radical; R is a straight or branched chain alkyl radical containing from 1 to 4 to 12 carbon atoms, and which may be the same or different from R, a straight or branched chain -radical alkenyl containing from 2 to 12 carbon atoms , preferably, from 4 to 8 carbon atoms, and more preferably an alkenyl radical derived from the conjugated diene of starting material to be carbonylated; ey is an integer from 1 to 10, and preferably less than or equal to 6. Examples of the quaternary onium cations that have the structural formula II, the following are representative tetramethi ammonium, trieti l eti onio, tributi lmeti 1 io amon, tri eti 1 (n offe 1) ammonium tetraeti lamon io, i lamonio tetrabut dodecyl - eti tri lamonio, meti ltriocti lamon io, io hepti 1 Tributi lamon, tetra propi 1 io amon, tetrapenti 1 amon io, tetrahexi lamon io, tetrahept i1 love child, tetraoct i lamon io, tetradeci lamon io, buti ltr i pROPI 1 ammonium me you LTRI uti lamonio, pentiltributi lamonio, METI ldieti lpropi lamonio, eti ldimeti lpropi lamonio, tetradodeci lamonio , ammonium tetraoctadecil hexadec i eti lamonio Itri, benz i Itrimeti lamonio, benci ldimeti lpro- pilamonio, benci ldimeti loct i lamonio, benci ltr i buty lamonio, bencU Triet i1 ammonium pheny Itrimeti lamonio, benci ldimeti ltetradec i 1 i ammonium -benz ldimeti 1 hexadec i 1 amonio, dime i Idif in i 1 ammonium, methyltrial- -qui 1 (Cg-C, 0) ammonium, methytrifeniumlammonium. buten-2-ltrieti lamonium, N, N-dimethyl-tetramethiine, nonane, N, N-diethyl-tetramethylene-ammonium, tetramethylphosphonium, tetrabutylphosphonium, ettrimeti-1-phosphonium, trimethyl-stypentylphosphonium, trimethylpentylphosphonium, octyltrimethyphosphonium, dodec Itrimeti lfosfonio, trimetil feni lfosfonio, dieti Id imeti lfosfonio, diciclohexi Id imeti lfosfon io, dimeti Idifeni lfosfonio, cyclo hexi Itrimeti lfosfonio, trieti lmeti lfosfonio, methyl-tri (isopropil) fosfonio, methyl-tri (n-propil) fosfonio, methyl-tri (n-butyl) phosphonium methyl-tri (2-methylpropyl) phosphonium, meti ltriciclohexi lfosfonio, meti ltrifeni lfosfonio, meti ltribenc i lfosfonio, methy 1-tri (4-methyl pheny 1) phosphonium meti ltrixi 1 i lfosfonio , DIETI lmeti lfeni lfosfonio, - i i lmeti benz lfosfonio pheny 1, ethyltriphenylphosphonium tetraetilfosfo-nio, eti 1-tri (n-propi 1) phosphonium trieti lpenti lfosfonio, hexadecU Tributi lfosfonio, ethyltriphenylphosphonium, n-buty 1-tri (n-propi 1) phosphonium, buti ltrifeni lfosfonio, benci ltrifen i lfosfonio (beta-phenylethyl) dimetilfen i lfosfonio, tetrafeni lfosfonio, trifeni 1 (4-methy 1 nil fe) phosphonium, tetrakis (hydroxymethyl) phosphonium, tetrakis (2-hidroxj_ et i 1) Phosfon io and tetrafen i larson io . And exemplary of the catioins of Formula V are the following: N-met i 1 pi r i f i n io, N-et i 1 pi r i di nio, N-hexadeci 1 pi r i -dinio and N-met i 1 picol inio. Among the cations having the structural formula V, the following are representative: 1, 2-bi s (tr imeti 1 ammon io) ethane 1, 3-bi s (trimeti 1 ammon io) propane, 1, 4-bi s ( trimethylammonium) butane and -1, 3-bi s (t imeti 1 ammonium) butane. Representative anions of onium salts include the following ions: F ", C10", FPg ~, BF 4? ~, Tetraphenyl borate anion, P04"3, HP04" 2, H2P04", CH-SO ~ HS04", N03", S04".Cl", and Br ". Preferably, the anion is Cl" or Br. "A particularly preferred onium salt used is tetrabutylammonium bromide. Speaking in general terms, the amount of onium salt will vary from approximately 0.1 to 10 per-hundred molar, relative to the compound of formula II, with a scale from 1 to 5 per cent. molar percent being preferred.Where the phase transfer catalyst can be added to the reaction at any time, from a practical point of view, the catalyst is preferably added to the reaction mixture all at once or in portions at a temperature between 65-909 C as a solid or a concentrated aqueous solution (40-50%) The process of the present invention utilizes an aqueous system, however, an aqueous / organic two-phase system may optionally be used. In fact, it is preferred to use an aqueous / organic system because the presence of the organic phase aids in phase separation at the termination of the reaction. When the organic phase is used, preferably the solid compound is pre-dissolved in the organic phase before addition to the hydrosulphide and sulfur. Representative examples of organic solvents include toluene, xylene, benzene, heptane, -octane, decane, chlorobenzene and the like. As mentioned above, the process of the invention is conducted in the presence of an aqueous phase. The volume of water that is present may vary. Preferably, the ammonium hydroxide or alkali metal hydrosulphide and sulfur are substantially dissolved or dispersed in the aqueous phase prior to the reaction with the silane compound of the formula II. The concentration of the two reagents in the aqueous phase generally varies from about 20 to 50 weight percent. Preferably, the concentration of the sulfur and sulfur in the aqueous phase ranges from approximately 25 to 45 percent. The process of the present invention is preferably conducted in the presence of an aqueous phase and a salt of the formula XY (VI) X2 S04 (VI1) where X is selected from the group consisting of Li, Na K, Rb and C ^; and wherein Y is selected from the group consisting of F, Cl and Br. Representative examples of these include LiF, LiCl, LiBr, L i 2S04 »NaF > NaCl, NaBr, Na2SO4, KF, KC1, KBr, K2S04, RbCl, RbBr, Rb2S04 > CsCl, CsBr and Cs2S04. While the amount of salt may vary, the salt is generally present in an amount ranging from 10 percent by weight of the aqueous solution to complete saturation of the aqueous solution Obviously, an excess of salt (rather than complete saturation) can be used; however, no additional benefit has been found. Also, as can be seen, all the different salts I n T5 'cited above have varying levels of solubility in an aqueous solution; however, the solubility of these salts is well known. In the context of saturation of the aqueous phase, - it must be calculated at the desired reaction temperature, since the solubility of these salts in an aqueous phase is related with the temperature of the aqueous phase. Preferably, the amount of salt that is present in the aqueous phase ranges from 20 weight percent to full saturation. The salt can be added to the reaction vessel at any time as long as it is present during the reaction. In accordance with the preferred embodiment of the present invention, the hydrosulfide, sulfur and salt are dissolved or dispersed in the aqueous phase. A solvent such as toluene or xylene is then added, followed by the silane compound of formula II. The mixture is then heated, optionally under an inert atmosphere. The mixture can be heated to a temperature ranging from about 60 to 100 ° C, with a temperature of 75 to 95 ° C being preferred. The appropriate amount of phase transfer catalyst is then added to the reaction mixture as a solid or as a concentrated aqueous solution. The progress of the reaction can then be followed by G.C. or other analytical techniques. During filtration, the filtrate is separated to the aqueous phase and organic phase containing the desired product. Any unreacted reagents and / or solvent are removed from the organic phase by purification under reduced pressure to provide the desired product as the container residue. In addition to the hydrosulfide, sulfur and silane, a reagent -additional of the formula: Alk-X (VIII) wherein X is defined above, it may be present in those cases where the non-symmetrical organo-1 compounds are desired in addition to those aforementioned bisorganosium compounds. The non-symmetrical organosilicon compounds are of the formula Alk- Al k- (IX) wherein n, Alk and Z are as defined above. As can be seen, Alk is a divalent hydrocarbon of 1 to 18 carbon atoms; and, therefore, to avoid duplication, the list -representative of asymmetric compounds incorporates "alkyl" in its name, while one skilled in the art observes -which would be methyl, ethyl, propyl, butyl, etc., and even octildec_i_ lo, depending on the reagents used. These non-symmetrical represetnati compounds include: 3-bi s (trimethoxy si 1 i 1 propi 1) n-alkyl disulfide, 3-bi s (trietoxy si 1 i 1 propyl) n-alkyl tetrasulfide, 3-bi octasulfide s (triethoxy if 1 i 1 propi 1) n-alkylo, tetrasulfide of 3-bi s (trimethoxy si 1 i 1 propi 1) n-alkyl, tetrasulfide of 2-bis (trietoxisi 1 i leti 1) n-alkyl, 3-bis (trimetoxisi 1 i lpropi 1) n-alkyl trisulphide, 3-bi s trisulfide (tr ietoxj_ silyl pro pyl) n-alkyl, 3-bi s disulfide (tributoxy si 1 i propyl) n-alkyl , 3-bi s hexasulfide (trimethoxy si 1 ipropi 1) n-alkyl, 3-bi s octasulfide (trimethoxy si 1 lpropi 1) n-alkyl, 3-bis tetrasulfide (triocotoxisi 1 i lpropi 1) n -alkyl, 3-bis- (tribexoxisi 1 i lpropi 1) n-alkyl disulfide, 3-bis (tri-sooc-toxisi 1 i lpropi 1) n-alkyl, 3-bis disulfide (tri-t- butoxy if 1 i 1 -propyl) n-alkyl, 2-bis (methoxy diethoxy silyl ethyl) n-alkyl tetrauslfuride, β-2- pentasulfide bi s (tri propoxy si 1 i leti 1) n-alkyl, tetrasulfide of 3-bis (tricyclohexoxi si 1 ipropi 1) n-alkyl trisulfuro of 3-bis (triciclopentoxisi 1 i lpropi 1) n-quilo, disulfuro de 2 -bis (d imet i 1 methoxy si 1 i leti 1) n-alkyl, 2-bis trisulfide (dimeti 1 sec. butoxy if 1 i leti 1) n-alkyl. tetrasulfide of 3-bis (methyl 1 but i letoxy if 1 i 1 propi 1) n alkyl, tetrasulfide of 3-bi s (di-t-buty lmetoxy si 1 ipropi 1) n alkyl, trisulfide of 2-bis (phenyl) methyl methoxy si 1 i leti 1) n-alkyl, tetrasulfide of 3-bis (d_ phenyl i sopropoxy si 1 i Ipropi 1) n-alkyl, disulfide of 3-bis (diphenyl-cyclohexoxi si 1 ipropi 1) n- alkyl, 3-bis tetrasulfide (dimethyl eti lmercaptosi 1 i Ipropi 1) n-alkyl, 2-bis (methy1 dimexosi 1 i leti 1) n-alkyl trisulfide, 2- bis (meth i 1 ethoxypropyl) tetrasulfide poxi si 1 i leti 1) n-alkyl, tetrasulfide of 3-bis (di et i 1 metoxisi-lilpropyl) n-alkyl, disulfide of 3-bis (et i 1 di-sec. butox isi 1 iJ_ propil) n- alkyl, 3-bis (propyl diethoxy if 1 i 1 propi 1) n-alkyl disulfide, 3-tbis (butyl dimethoxy if 1 i 1 propi 1) n-alkylate trisulfide, 3-bis (fen i 1 dimethoxy) tetrasulfide if 1 i 1 propi 1) n-alkyl tetrasulfide of 4-bi s (trimethoxy si 1 i lbuti 1) n-alkyl, tetrasulfide of 6-bi s (triethoxy if 1 ihex 1) n-alkyl, disulfide of 12-bis- (tri i sopropoxy if 1 i 1 dodecyl) n-alkyl, tetrasulfide of 18-bis- (trimethoxy si 1 i loctadeci 1) n-alkyl, tetrasulfide of 18-bis (tri-propoxy si 1 i loctadeceni 1) n-alkyl, tetrasulfide of 4-bi s (tripet xi 1 i 1 -buten-2 i 1) n-alkyl, ether sulfide of 4-bi s (trimethoxy si-1 i-cyclohexyl) n-alkyl, 5-bi s trisulfide (dimethoxymethyl-1-ylpentyl) n-alkyl, tetrasulfide of 3-bi s (trimethoxy si 1 i 1 -2- methylpropyl) n-alkyl and disulfide of 3-bi s (dimethoxypheni 1 si 1 i 1 -2-me ti lpropi 1) n-alkyi. This invention is illustrated by the following working example which is presented merely for the purpose of illustration and is not intended to be limiting of the scope of the invention, unless specifically indicated otherwise, the parts and percentages are provided in weight.

EXAMPLE 1 Control Reaction of 3-Cloropropi Itriethoxy Si Tin and Sodium Hydrosulfide In a round bottom flask, three-necked, one-liter capacity, equipped with a mechanical teflon blade agitator, a thermometer and a condenser, were loaded with 45.0 g (0.59 moles) of sodium hydrosulfide flake from PPG ^ (test nominally 73.5 percent NaSH), 50 ml of saturated sodium chloride solution, 50 ml of toluene and 240.0 g (0.10 moles of 3-chloropropytrietoxy if tin (CPTES) .The mixture was then stirred at 430-470 rpm while heating to 85 ° C. At this temperature, 1.0 g (0.031 mole) of tetrabutyl bromide bromide phase transformation catalyst was added as a solid all the time to the reaction mixture. Immediately color Within 2 minutes, the originally pale yellow aqueous phase had turned to water white at the temperature of the reaction mixture had risen to about 925 ° C. After 15 minutes, the reaction mixture was analyzed by gas chromatography (gc) and encounter It found that it contains -20 percent of starting CPTES, 64.9 percent of 3-mercaptopropyl ltriethoxysilane (MPTES), 10-1 percent of monosulfide of -3, 3 '-bi s- (trietoxisi 1 i Ipropi) (TESPM) and 5.0 percent of dij_furo of 3, 3 '-bis- (trietoxi si 1 i 1 propi lo) (TESPED).

Example 2 Reaction of CPTES, NaSH and Sulfur The reaction was repeated as described in Example 1, except that 0.4 g (0.0125 moles) of sulfur elemen was added to the reaction mixture. After the addition of the phase transfer catalyst, the reaction mixture became dark green in color. This color fades to pale yellow-green within 10-15 minutes. After a reaction time of 15 minutes, the anal i s i of g.c. indicated a composition of 12.8 percent of starting CPTES, 55.5 percent of MPTES, 31.6 percent of TESPD and a vestige of TESPM.

Example 3 Reaction of CPTES, NaSH and Sulfur The reaction was repeated as described in Example 1 except that 0.8 g (0.025 mole) of elemental sulfur was added to the reaction mixture. Again, a green-dark color was observed after the addition of the catalyst. After a 15 minute reaction time, the g.c. indicated a composition of 4.4 percent tri-n-butylam (a catalyst decomposition product), 41.1 of MPTES, 52.0 of TESPD and -T 2.5 percent of an unknown. Only vestiges of CPTES and TESPM were detected.

Example 4 Reaction of CPTES, NaSH and Sulfur The reaction was repeated as described in Example 1 except that 1.2 g (0.0375 mole) of elemental sulfur was added to the reaction mixture. After a 15-minute reaction time, the g.c. indicated a composition of 3.7 percent tri-n-butylamine, 19.1 percent MPTES, 77.1 percent TESPD, vestigial quantities of CPTES, TESPM and trisulfide of 3, 3 '-bi s- (trietoxy if 1 i lpropi lo) were also detected (TESPT).

Example 5 Reaction of CPTES, NaSH and Sulfur The reaction was repeated as described in Example 1 except that 1.6 g (0.05 mole) of elemental sulfur was added to the reaction mixture. After a reaction time of 15 minutes, the analysis of g.c. indicated a composition of 3.1 for tri-n-buti lamina, 26.3 percent for MPTES, 63.0 for TESPD and 7.5 for TESPT. Trace amounts of CPTES and TESPM were also detected.

Example 6 Reaction of CPTES, NaSH and Sulfur The reaction was repeated as described in Example 1 except that 7.8 g (0.10 moles of NaSH PPG ^ scale, 3.2 g (0.10 moles) of elemental sulfur and 24.0 g (0.10 g) were added. moles of CPTES.When adding the catalyst to 859C, the color of the mixture became dark red which gradually faded to a lighter red for a period of 30 minutes. 13 nmr C and proton of the product indicated a composition of 35-mole percent of TESPD, 35 percent mole of TESPT and 30 mole percent of higher polysulfides.

Example 7 Reaction of CPTES, NaSH and Sulfur The reaction described in Example 1 was repeated except that 7.8 g (0.10 mole of NaSH PPAG scale ^ ^, 9.6 g (0.3 mole) of elemental sulfur and 24.0 g (0.10 mole) were used. After adding the catalyst at 85 ° C, the color of the mixture became blackish red.The reaction was carried out for 30 minutes at 85 ° C. The lower aqueous phase became colorless and the upper organic phase dark red. The analysis of protonoes and rmn C of the product indicated a composition of 11.8 percent by weight of TESPD, 28. 8 percent by weight of TESPT, 29.0 percent by weight of tetrasulfide, 16.5 percent by weight of pentasulfide, 9.7 percent by weight of hexasulfide, and 4.2 percent by weight of higher polysulfide.

EXAMPLE 8 Preparation of a 3'3'-bistriethoxy-1-1-n-butyl disulfide-containing mixture and (3-tethoxy if 1-1-propyl-1-n-butyl) disulfide The reaction was repeated as described in Example 1 in a similar manner, except that 1.2 g (0.0372 mole) of elemental sulfur was added to the reaction mixture and 12.0 g (0.05-mole) of the original charge of 24.0 g of CPTES were replaced with 4.75 g ( 0.05 moles) of 1-chlorobutane. The mixture was heated to 85 ° C and 2.0 g of a 50 percent aqueous solution of tetrabutyl ammonium bromide (0.0031 mol) were added all at once. The reaction mixture became immediately greenish black in color and the reaction temperature increased to approximately 939C before being slowly subdivided. After a reaction time of 30 minutes, the color of the lower aqueous phase had faded to an orange green. The g.c. of the toluene phase of the mixture indicated a composition of 6.1 percent tri-n-buty 1 amine, 15.3 percent n-butyl disulfide, 6.1 percent MPTES, 45.4 percent mixed disulfide, disulphide ( trietoxi si 1 i lpropi 1) n-butyl or TEPBD and 27.0 percent of TESPD. The colorless toluene phase was separated. The toluene was then removed under reduced pressure to provide 17.85 g of crude product.

EXAMPLE 9 Preparation of a mixture containing 3, 3 '-bi s- (triethoxysi 1 lpropyl) disulfide and (3-tethoxy if 1 i 1 propi 1) n-butyl disulfide. The reaction was repeated as described. described in Example 8 at a scale of 10X. The G.C. of the toluene phase of the mixture indicated a composition of 5.9 percent of tr i -n-but ij_ amine, 14.1 percent of n-butyl disulfide, 12.0 percent of MPTES, 44.0 percent of the mixed disulfide (disulfide of (3-triethoxysi 1 i-propyl) n-butyl, TEPBD and 24.0 percent of TESPD The colorless toluene phase was separated.Toluene was then extracted under reduced pressure (68.58 cm Hg) to provide 158.5 g of crude product The crude product was then deputed to high vacuum (0.15 mm Hg) at a total temperature of 110 QC). The analysis of c.g. of the container residue indicated a composition of approximately 61.5 percent TEPBD and 38.5 percent TESPD. The weight of the container residue was 110 g of an almost colorless H. After cooling, the orange aqueous phase at room temperature, sodium chloride was precipitated. The salt was separated by filtration and the aqueous phase (854 g) was saved for recycling in Example 10 * EXAMPLE 10 Preparation of a mixture containing 3, 3 '-bi s- (triethoxysi 1 lpropyl) disulphide and (3-triethoxy si 1 lpropyl) n -butyl disulfide The reaction was repeated as described in Example 9 except that 854 g of the aqueous recirculation of Pipe 9 was charged to the reactor together with 76 g of 73% percent pure NaSH (1.0 mol) and 12.0 g (0.375 mol) of sulfur. The analysis of g.c. of the toluene phase of the mixture after reacting for 30 minutes indicated a composition of 63. percent of tri-n-butylamine, 14.6 percent of n-butyl disulfide, 10.6 percent of MPTES, 44.4 percent percent mixed disulfide, disulfide of (3-trietoxy si 1 ipropro) n-butyl, TEPBD and 24.1 percent of TESPD. The toluene / top product phase was separated from the aqueous phase while the mixture was still heated. Upon cooling, at room temperature, the orange aqueous phase, sodium chloride, was precipitated. The salt was removed by filtration and the aqueous phase - (870 g) was saved for recycling in Example 11.

EXAMPLE 11 Preparation of a 3,3 '-bis- (triethoxysi-1-propyl) disulphide mixture and (3-triethoxysi-1-propyl) n-butyl disulphide The reaction was repeated as described in Example 9 except that 870 g of the aqueous recirculation of Pipe 10 was charged to the reactor, together with 76 g of pure NaSH at 73.5 percent (1.0 mol) and 12.0 g (0.375 mol) of sulfur. The analysis of g.c. of the toluene phase of the mixture after reaction for 30 minutes indicated a composition of 6.0 percent of tr i -n-buty 1 to mine, 14.5 percent of n-butyl disulfide, 10.0 percent of MPTES, 43.6 percent percent of mixed disulfide, disulfide of (3-tr ethoxysi 1 i Ipropi) nObutyl, TEPBD and 25.9 percent of TESPD. The toluene / top product phase was separated from the aqueous phase while the mixture was still hot. After cooling to room temperature, the aqueous phase is orange, precipitated sodium chloride. The salt was removed by filtration and the aqueous phase (878 g) was saved for recirculation in Example 12.

EXAMPLE 12 Preparation of a 3,3 '-bis- (triethoxysi-1-propyl) -disulfide-containing mixture and (3-triethoxy if 1-propyl) -butylidene sulfide. The reaction was repeated as described in Example except that 878 g of the aqueous recirculation of the pious Axis 11 was charged to the reactor together with 76 g of 73.5 percent pure NaSH (1.0 mol) and 12.0 g (0.375 mol) of sulfur. The analysis of g.c. of the toluene phase of the mixture after reacting for 30 minutes indicated a composition of 6.8 percent of tri-n-bu tilamine, 15.0 percent of n-butyl disulfide, 10.3 percent of MPTES, 44.0 percent of mixed disulfide, (3-triethoxysi-1-propyl) n-butyl disulfide, TEPBD and 23.9 percent TESPD The upper phase of toluene / product was separated from the aqueous phase while the mixture was still hot. Upon cooling to room temperature, the orange aqueous phase, sodium ride was precipitated. These examples demonstrate two things. First, that a high level of trialkoxy-si-1-1-propyl-1-n-alkylated disulfide (as a statistical mixture) can easily be prepared by this phase transfer technique. Secondly, the aqueous phase can be recirculated at least three times to provide essentially the same product composition by adding - just enough sodium hydrosulfide and sulfur at each recirculation to compensate for that converted into disulfides in the previous run. Mixed disulfides containing trialkoxysi 1-1-n-alkylalkyl disulphide may provide higher cost processing and costs in mixtures of acetic acid with those obtained from bis-silanes. that contain more conventional sulfur. Although certain modalities and representative details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the scope or scope of the invention.

Claims (10)

1. - A process for the production of or-ganosilicon compounds of the formula: where Z is selected from the group consisting of 1 1 R Si- Si-R 'Si-R' l 2 R i 2 ¿Í2 wherein R is an alkyl group of 1 to 4 carbon atoms, cyclohexy lo or phenol; 2 R is alkoxy of 1 to 8 carbon atoms, or cycloalkoxy of 5 to 8 carbon atoms; Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and n is an integer of 2 to 8; characterized by reacting (A) a compound of the formula:

Z-Alk-X (ID when X is Cl or Br; with (B) an ammonium hydrosulphide or alkali metal hydro- sulfide and (C) sulfur; wherein the reaction is conducted in the presence of a phase transfer catcher and an aqueous phase. 2. The process of claim 1, characterized in that the reaction is carried out at a temperature ranging from 60 ° C to 100 ° C.

3. The process of claim 1, characterized in that the reaction is conducted in the presence of an aqueous phase and an organic phase. 4. The process of claim 1, characterized in that the phase transfer catalyst is selected from the formulas: R (III) 10 (IV) 11 (R12) (CH2) and (R9) (V) 13 13

4 6 wherein A represents nitrogen, phosphorus or arsenic; R, Rr, R, R, which may be the same or different, are each a straight or branched chain alkyl radical containing from 1 to 16 carbon atoms, optionally substituted with a n -yl, hydroxyl, halo, nitro, alkoxy or coxycarbon substituent.; a straight or branched chain alkenyl radical containing from 2 to 12 carbon atoms; an aryl radical containing from 6 to 10 carbon atoms, optionally substituted by one or more alkyl substituents containing from 1 to 4 carbon atoms or substituents alkoxy, alkoxycarbonyl or halo; and with the proviso that any two of the radicals R to R can together form a single alkylene, alkenylene or alkaline radical of chain Q neal or branched chain containing from 3 to 6 carbon atoms, R, RR 10, R 11, which may also be the same or different, are each - a straight or branched chain alkyl radical containing from 1 to 4 carbon atoms; with the condition that the 10 111 R and R can together form an alkylene radical containing from 3 to 6 carbon atoms; and with the additional proviso - that R 9 and R 10 or R 9 and R 11 can together form an alkylene, alkenylene or alkadiene radical containing 4 carbon atoms, and together with the nitrogen atom, which comprises nitrogen 12 heterocycle of 5 members; R is a straight or branched chain alkyl radical containing from 1 to 4 carbon atoms; or - 13 a phenyl radical; R is a straight or branched chain alkyl radical containing from 1 to 4 carbon atoms, and which can be -12 equal to or different from R, a straight or branched chain alkenyl radical containing from 2 to 12 carbon atoms; and y is an integer greater than or equal to 1 and less than or equal to 10.

5. The process of claim 1, characterized in that the phase transfer catalyst of tertiary butyl ammonium bromide.

6. - The process of claim 3, characterized in that an organic solvent is selected from the group consisting of toluene, xylene, benzene, hpetane, octane, decane, chlorobenzene and the like.

7. The process of claim 1, characterized in that the reaction is conducted in the presence of a salt of one of the following formulas X Y (VI) x2 so4 (VII) wherein X is selected from the group consisting of Li, Na, K, Rb and Cs; and wherein Y is selected from the group consisting of Fl, Cl and Br. The process of claim 7, characterized in that the salt is present in an amount ranging from 10 percent by weight of the aqueous solution to complete saturation of the aqueous solution. 9. The process of claim 1, characterized in that, in addition to the reactants (A), (B) and (C), a compound (D) is present and is of the formula: Alk-X (VIII) 10. The process of claim 9, characterized in that the molar ratio of the compound of the formula II to the compound of the formula VIII varies from 99: 1 to 1: 1.