CN100584849C - Process for the preparation of mercaptoorganyl (alkoxysilanes) - Google Patents

Process for the preparation of mercaptoorganyl (alkoxysilanes) Download PDF

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CN100584849C
CN100584849C CN200510103601A CN200510103601A CN100584849C CN 100584849 C CN100584849 C CN 100584849C CN 200510103601 A CN200510103601 A CN 200510103601A CN 200510103601 A CN200510103601 A CN 200510103601A CN 100584849 C CN100584849 C CN 100584849C
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thiol group
organic radical
organoalkoxysilane
group
order
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CN1746177A (en
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卡斯滕·科尔特
菲利普·阿尔贝特
多里特·沃尔夫
斯特芬·泽巴尔德
雷蒙德·彼得
阿尔弗雷德·阿里格
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Evonik Operations GmbH
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Degussa GmbH
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Abstract

The invention relates to a process for the preparation of mercaptoorganyl(alkoxysilanes), wherein bis(alkoxysilylorganyl)polysulfides are hydrogenated with hydrogen and a transition metal catalyst in a solvent without the addition of alcohols, H<SUB>2</SUB>S or water.

Description

In order to make the method for thiol group organic radical (organoalkoxysilane)
Technical field
The present invention relates to a kind of in order to make the method for thiol group organic radical (organoalkoxysilane).
Background technology
US 6,147,242 disclose a kind of by two (alkoxysilyl organic radical) disulphide are evenly decomposed to make the method for 3-thiol group propyl group-triethoxyl silane.This method comprises makes two (alkoxysilyl organic radical) disulphide and a kind of basic metal and the reaction of a kind of chlorosilane to make silyl alkyl sulfane base silane intermediate product, and the reaction under the situation that alcohol exists of this intermediate product generates the thiol group alkyl silane of expectation then.
The shortcoming of this method is must use extra reagent (chlorine alkyl silane), and need to use dangerous basic metal and removed, and silyl alkyl sulfane base silane intermediate product to need to be separated before the alcoholysis step.
In addition, US 6,433,206 disclose a kind of under the situation of using the group VIII metal catalyst by making two (organic radical silyl) polysulphide generation hydrogenizations making the method for siliceous organic mercaptan, this catalyzer must be before poisoning water, H 2S or alcohol are protected.
The shortcoming of this method is, if use with the pure different alcohol that is used for the substituted alcoxyl base silane as poisoning inhibitor or the catalyzer reagent that detoxifies, then transesterify can take place in the Siliciumatom of the product of the Siliciumatom of used reactant and generation, produces the mixing esterification silane product of non-expectation thus.Therefore, for viewpoint actual and economically, add detoxifcation reagent and be confined to these alcohol as the alkoxysilyl in the reactant.
Other shortcomings of this method are, (＞C8) organoalkoxysilane is as initial substance if use and to have long-chain alkoxy base substituting group, then the removing and the fractionation by distillation of the alcohol that needs as detoxifcation reagent place make energy consumption increase De Genggao, and therefore need higher technology and more complicated.
Alcohol as detoxifcation reagent is as oxygen affinity nuclear reagent, for polysulfanes base silane with various replacement forms, can not as or expectation become requisite detoxifcation reagent during the hydrogenization, this is because it can form by product.
Use requisite alcohol as detoxifcation reagent, make the selection of possible initial substance be restricted.This shortcoming of disclosed method also have, H is only arranged 2S or water can be used as the surrogate of alcohol.H 2S is highly toxic gas, and it uses, stores, adds and removing needs highly careful, as to prepare to accept the risk, need height equipment quality and device security.Should avoid making water when using organoalkoxysilane at the same time, this is because initial compounds and product compound can be destroyed under hydrolytic action.
Summary of the invention
The purpose of this invention is to provide a kind of method that makes two (alkoxysilyl organic radical) polysulphide generation reductive cleavage reactions, this method is not used the required extra detoxifcation reagent of metal catalyst, as water, alcohol or hydrogen sulfide, and can realize high conversion.
The present invention relates to a kind of method, it is characterized in that, in a kind of solvent, do not adding alcohol, H in order to manufacturing thiol group organic radical (organoalkoxysilane) 2Make two (alkoxysilyl organic radical) polysulphide generation hydrogenizations with hydrogen and transition-metal catalyst under the situation of S or water.
The usage quantity of this solvent can be 0.1 to 80 weight %, is preferably 1 to 50 weight % especially, most preferably is 1 to 30 weight %.
This reaction preferably can be implemented under no air and anhydrous situation.
Solvent for use can prolong the work-ing life of catalyst system therefor.Solvent for use can make the simpler or use with improvement of catalyst system therefor.Solvent for use can improve the reusability of catalyst system therefor.
The boiling point of solvent for use can be-50 to 250 ℃, is preferably 0 to 150 ℃, is preferably 20 to 100 ℃ especially.
Dewater and H 2Beyond the S, the compound that can use all non-alcohols is as solvent.
Preferably can use the non-alcohol compound of straight chain type, branching type or ring-type that contains Sauerstoffatom, sulphur atom, phosphorus atom or nitrogen-atoms as solvent.
Especially preferably can use alkane, ether, amine, mercaptan, dialkyl sulfide or alkyl phosphine (Alkylphosphane).
The thiol group alkyl (organoalkoxysilane) that most preferably can use Anaesthetie Ether, methyl tertiary butyl ether, tetrahydrofuran (THF), diox, carbonic acid gas (liquid or as supercritical liq), ammonia, pentane, hexane, heptane, octane, DMF or generate as product.
This solvent can be the combination or the mixture of ion type liquid or ion type liquid.
Used ion type liquid can be used as co-catalyst.
Used ion type liquid can improve transformation efficiency.
Used ion type liquid can improve activity.
Used ion type liquid can improve selectivity.
The fusing point of used ion type liquid can be 0 to 250 ℃, is preferably 50 to 180 ℃, is preferably 80 to 150 ℃ especially.
Ion type liquid can be by containing a kind of positively charged ion and a kind of anionic homogeneous phase compound formation.Ion type liquid can be by containing more kinds of positively charged ions and more kinds of anionic compound formation.Ion type liquid can be by containing a kind of positively charged ion and more kinds of anionic compound formation.Ion type liquid can be by containing more kinds of positively charged ions and a kind of anionic compound formation.
Ion type liquid can contain a kind of salt, promptly at least a positively charged ion and at least a negatively charged ion, and it is in a liquid state under selected reaction conditions.
Ion type liquid can have low-down vapour pressure (in theory near zero), and this is favourable for many application scenarios.
Ion type liquid can comprise organic salt, the salt of preferred package heterocyclic nitrogen containing compound.
Ion type liquid can contain alkylation or polyalkylated assorted aromatic hydrocarbons.Alkylation or polyalkylated assorted aromatic hydrocarbons can be alkylating pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles, oxazole or triazole.This alkyl substituent can have the chain length of C1-C40, and for straight chain type, branching type or be substituted.This alkyl substituent can be identical or different.
Ion type liquid can contain the ammonium N (alkyl) that is substituted 3(R ') (+), 1,3-dialkylimidazolium salt ion or phosphonium ion P{ alkyl } 3(R ') (+)Salt.
Positively charged ion can use for example cationic bmim, bm 2Im, emim, ommim, mmim, bupy, C 6Py, C 8Py, N 8,8,8,1, N 6,2,2,2, [MeNEt 3], [MeNBu 3], [MeNPent 3] and [MeNHex 3].
These positively charged ions can have one or more positive charges.These negatively charged ion can have one or more negative charges.
Negatively charged ion can use phosphoric acid salt, acid amides, vitriol, tetrachloro (aluminate), sulphite, nitrate, nitrite, alkyl-sulphate, alkylsulfonate or halogenide.
Negatively charged ion can use for example muriate, bromide, iodide, HSO 4 (-), BF 4 (-), BCl 4 (-), PF 6 (-), ASF 6 (-), SbF 6 (-), HCO 3 (-), lactic acid salt, asccharin hydrochlorate, Al (Cl) 4 (-), Al 2(Cl) 7 (-), Al 3Cl 10 (-), CuCl 2 (-), Cu 2Cl 3 (-), Cu 3Cl 4 (-), SnCl 3 (-), Sn 2Cl 5 (-), CH 3-SO 4 (-), CH 3-CH 2-SO 4 (-), CF 3-SO 3 (-), CH 3-SO 3 (-), CF 3-COO (-), C 8H 17-(SO 4) (-), C 16H 33-(SO 4) (-), two [(trifluoromethyl) alkylsulfonyl] acid amides, tosylate.
Ion type liquid can use for example LiAlCl 4-AlCl 3, NaAlCl 4-AlCl 3, KAlCl 4-AlCl 3, MgAlCl 4-AlCl 3, NaAlCl 4-KAlCl 4, NaAlCl 4-KAlCl 4-AlCl 3, NaAlCl 4-KAlCl 4-MgCl 2, KAlCl 4-Ca (AlCl 4) 2Or NaAlCl 4-KAlCl 4-LiAlCl 4Mixture.Preferably can use the eutectic of these mixtures or near the mixture of its eutectic point.
Ion type liquid can use for example LiAlCl 4, NaAlCl 4, KAlCl 4, Mg{AlCl 4} 2Or Ca (AlCl 4) 2
These positively charged ions and negatively charged ion can meet P.Wasserscheid and W.Keim at Angew.Chem.Int.Ed.2000, the description in 39,3773.
These positively charged ions and negatively charged ion can meet T.Welton at Chem.Rev.1999, the description in 99,2071.
This treats that two (alkoxysilyl organic radical) polysulphides of hydrogenant can mix with polarity or nonpolar, proton type or non-proton type material.
This pair (alkoxysilyl organic radical) polysulphide can be the compound of general formula (I):
Z-A-S x-A-Z (I)
Wherein,
X is 1 to 14 number, is preferably 1 to 8, more preferably 2 to 4, be preferably 2 to 2.6 especially, and Z is identical or different, and is SiX 1X 2X 3Or Si (OCH 2-CH 2-) 3N, and
X 1, X 2, X 3All can be mutually irrelevantly representation hydroxy is (OH),
Have straight chain type, branching type or the cyclic hydrocarbon chain of 1 to 18 carbon atom (C1-C18), preferably have C1-C10, more preferably methyl, ethyl, propyl group or butyl,
Alkyl acid (C yH 2y+1)-C (=O) O-, y=1～25 wherein,
Thiazolinyl acid substituting group, for example acetoxyl group CH 3-(C=O) O-,
Alkyl acid substituting group that is substituted or thiazolinyl acid substituting group,
Cycloalkyl with 5 to 12 carbon atoms,
Phenmethyl, the phenyl that halogen replaces or alkyl replaces,
Alkoxyl group is preferably the (C with straight chain type or branching type hydrocarbon chain 1-C 24) alkoxyl group, more preferably methoxyl group (CH 3O-), oxyethyl group (C 2H 5O-), propoxy-(C 3H 7O-), butoxy (C 4H 9O-), dodecyloxy (C 12H 25O-), tetradecyloxyaniline (C 14H 29O-), n-Hexadecane oxygen base (C 16H 33O-) or octadecane oxygen base (C 18H 37O-),
Has (C 5-C 12) cycloalkyloxy of atom,
The phenoxy group that halogen replaces or alkyl replaces,
Benzyloxy,
Alkylether radicals O-(CR I 2-CR I 2)-O-Alk,
Alkyl, polyether base O-(CR I 2-CR I 2O) a-Alk, wherein a=2～25 are preferably a=2～15, are not preferably a=3～10, most preferably are a=3～6, R IIrrelevantly represent H or alkyl mutually, be preferably CH 3-Ji, Alk is preferably C1-C20 for having 1 to 30 carbon atom (C1-C30), straight chain type or branching type, saturated or undersaturated alkyl chain, is preferably C4-C18 especially, most preferably is C8-C16;
A is the two valency C that comprise straight chain type or branching type, saturated or unsaturated, aliphatic, aromatics or aliphatic series/aromatics mixed type 1-C 30Hydrocarbon chain is preferably C 1-C 3, (CH more preferably 2-), (CH 2-) 2, (CH 2-) 3, (CH (CH 3)-CH 2-) or (CH 2-CH (CH 3)-).
A can be straight chain type or branching type, and contains saturated bond and unsaturated link(age).A can not have the hydrogen substituting group and have various substituting group, for example-CN, halogen, as-Cl ,-Br or-F, alcohol functional group-OH, alkoxide.The preferred available CH of A 2, CH 2CH 2, CH 2CH 2CH 2, CH 2CH (CH 3), CH 2CH 2CH 2CH 2, CH 2CH 2CH (CH 3), CH 2CH (CH 3) CH 2, CH 2CH 2CH 2CH 2CH 2, CH 2CH (CH 3) CH 2CH 2, CH 2CH 2CH (CH 3) CH 2, CH (CH 3) CH 2CH (CH 3) or CH 2CH (CH 3) CH (CH 3).
The silane of general formula (I) can be used for example following compound:
Can be as required two (alkoxysilyl organic radical) polysulphides of initial substance and to have-S 1-to-S 14-two (alkoxysilyl organic radical) polysulphides or have two (alkoxysilyl organic radical) polysulphides of sulphur chain length.
Two (alkoxysilyl organic radical) polysulphide preferably can use mean chain length degree S x=S 2To S 2.7(S x-in x=2～14, its can by HPLC or 1H-NMR mensuration) two (alkoxysilyl organic radical) disulphide.
Group Z=SiX 1X 2X 3Preferably can be-Si (OMe) 3,-Si (OEt) 3,-SiMe (OMe) 2,-SiMe (OEt) 2) ,-SiMe 2(OMe) ,-SiMe 2(OEt) ,-Si (OC 12H 25) 3, Si (OC 14H 29) 3, Si (0C 16H 33) 3, Si (OC 18H 37) 3, Si (OC 14H 29) 2(OC 16H 33), Si (OC 14H 29) 2(OC 18H 37), Si (OC 16H 33) 2(OC 14H 29), Si (OC 16H 33) 2(OC 18H 37), Si (OC 18H 37) 2(OC 16H 33) or Si (OC 14H 29) (OC 18H 37) 2
Two (alkoxysilyl organic radical) polysulphide can be used Si266, Si 266/2, Si 261, Si 75 and the Si 69 of Degussa stock company, the Silquest A1589 of General Electric-Osi, Silquest A 1289 or Silquest A 15304, the KBE 846 of Shin-Etsu Chemical company limited or KBE 856, the Cabrus 4 of Daiso company limited, Cabrus 2A or Cabrus2B, or the HP 669 or the HP 1589 of Hung Pai Chemical company.
Depend on manufacturing processed, this pair (alkoxysilyl organic radical) polysulphide can contain the 3-chlorine organic radical (organoalkoxysilane) of 0.01 to 5 weight %.
Depend on manufacturing processed, this pair (alkoxysilyl organic radical) polysulphide can contain the elementary sulfur of 0.001 to 1 weight %.
Depend on manufacturing processed, this pair (alkoxysilyl organic radical) polysulphide can contain the alcohol of 0.001 to 1 weight %.
Formed thiol group organic radical (organoalkoxysilane) can be the compound of general formula (II)
Z-A-SH (II)
Wherein, Z and A all irrelevantly have mutually according to the described definition of formula (I).
Group-SiX in the formula (II) 1X 2X 3Preferably can be-Si (OMe) 3,-Si (OMe) 2OH ,-Si (OMe) is (OH) 2,-Si (OEt) 3,-Si (OEt) 2OH ,-Si (OEt) is (OH) 2,-SiMe (OMe) 2,-SiMe (OEt) 2) ,-SiMe (OH) 2,-SiMe 2(OMe) ,-SiMe 2(OEt), SiMe 2(OH) ,-Si[-O (CO) CH 3] 3,-Si (OC 12H 25) 3, Si (OC 14H 29) 3, Si (OC 16H 33) 3, Si (OC 18H 37) 3, Si (OC 14H 29) 2(OC 16H 33), Si (OC 14H 29) 2(OC 18H 37), Si (OC 16H 33) 2(OC 14H 29), Si (OC 16H 33) 2(OC 18H 37), Si (OC 18H 37) 2(OC 16H 33), Si (OC 14H 29) (OC 18H 37) 2
Formed thiol group organic radical (organoalkoxysilane) can be the mixture of general formula (II) compound.
For example, the thiol group organic radical (organoalkoxysilane) of general formula (II) can be:
3-thiol group propyl group (Trimethoxy silane),
3-thiol group propyl group (dimethoxy silicol),
3-thiol group propyl group (triethoxyl silane),
3-thiol group propyl group (diethoxy silicol),
3-thiol group propyl group (diethoxy methoxy silane),
3-thiol group propyl group (tripropoxy silane),
3-thiol group propyl group (dipropoxy methoxy silane),
3-thiol group propyl group (dipropoxy silicol),
3-thiol group propyl group (three dodecyloxy silane),
3-thiol group propyl group (two dodecyloxy silicol),
3-thiol group propyl group (three tetradecyloxyaniline silane),
3-thiol group propyl group (three n-Hexadecane TMOS),
3-thiol group propyl group (three octadecane TMOS),
3-thiol group propyl group (two dodecyloxy) tetradecyloxyaniline silane,
3-thiol group propyl group (dodecyloxy) tetradecyloxyaniline (n-Hexadecane oxygen base) silane,
3-thiol group propyl group (dimethoxy-methyl silane),
3-thiol group propyl group (methoxymethyl silicol),
3-thiol group propyl group (methoxyl group dimethylsilane),
3-thiol group propyl group (hydroxyl dimethylsilane),
3-thiol group propyl group (diethoxymethyl silane),
3-thiol group propyl group (oxyethyl group hydroxymethyl silane),
3-thiol group propyl group (oxyethyl group dimethylsilane),
3-thiol group propyl group (dipropoxy methyl-monosilane),
3-thiol group propyl group (propoxy-methyl silicol),
3-thiol group propyl group (propoxy-dimethylsilane),
3-thiol group propyl group (diisopropoxy methyl-monosilane),
3-thiol group propyl group (isopropoxy dimethylsilane),
3-thiol group propyl group (dibutoxy methyl-monosilane),
3-thiol group propyl group (butoxy dimethylsilane),
3-thiol group propyl group (two isobutoxy methyl-monosilanes),
3-thiol group propyl group (isobutoxy methyl silicol),
3-thiol group propyl group (isobutoxy dimethylsilane),
3-thiol group propyl group (two dodecyloxy methyl-monosilane),
3-thiol group propyl group (dodecyloxy dimethylsilane),
3-thiol group propyl group (two tetradecyloxyaniline methyl-monosilane),
3-thiol group propyl group (tetradecyloxyaniline methyl silicol),
3-thiol group propyl group (tetradecyloxyaniline dimethylsilane),
2-thiol group ethyl (Trimethoxy silane),
2-thiol group ethyl (triethoxyl silane),
2-thiol group ethyl (diethoxy methoxy silane),
2-thiol group ethyl (tripropoxy silane),
2-thiol group ethyl (dipropoxy methoxy silane),
2-thiol group ethyl (three dodecyloxy silane),
2-thiol group ethyl (three tetradecyloxyaniline silane),
2-thiol group ethyl (three n-Hexadecane TMOS),
2-thiol group ethyl (three octadecane TMOS),
2-thiol group ethyl (two dodecyloxy) tetradecyloxyaniline silane,
2-thiol group ethyl (dodecyloxy) tetradecyloxyaniline (n-Hexadecane oxygen base) silane,
2-thiol group ethyl (dimethoxy-methyl silane),
2-thiol group ethyl (methoxymethyl silicol),
2-thiol group ethyl (methoxyl group dimethylsilane),
2-thiol group ethyl (diethoxymethyl silane),
2-thiol group ethyl (oxyethyl group dimethylsilane),
2-thiol group ethyl (hydroxyl dimethylsilane),
1-thiol group methyl (Trimethoxy silane),
1-thiol group methyl (triethoxyl silane),
1-thiol group methyl (diethoxy methoxy silane),
1-thiol group methyl (diethoxy silicol),
1-thiol group methyl (dipropoxy methoxy silane),
1-thiol group methyl (tripropoxy silane),
1-thiol group methyl (Trimethoxy silane),
1-thiol group methyl (dimethoxy-methyl silane),
1-thiol group methyl (methoxyl group dimethylsilane),
1-thiol group methyl (diethoxymethyl silane),
1-thiol group methyl (ethoxyl methyl silicol),
1-thiol group methyl (oxyethyl group dimethylsilane),
3-thiol group butyl (Trimethoxy silane),
3-thiol group butyl (triethoxyl silane),
3-thiol group butyl (diethoxy methoxy silane),
3-thiol group butyl (tripropoxy silane),
3-thiol group butyl (dipropoxy methoxy silane),
3-thiol group butyl (dimethoxy-methyl silane),
3-thiol group butyl (diethoxymethyl silane),
3-thiol group butyl (dimethyl methyl TMOS),
3-thiol group butyl (dimethylethoxysilane),
3-thiol group butyl (dimethyl hydroxyl silane),
3-thiol group butyl (three dodecyloxy silane),
3-thiol group butyl (three tetradecyloxyaniline silane),
3-thiol group butyl (three n-Hexadecane TMOS),
3-thiol group butyl (two dodecyloxy) tetradecyloxyaniline silane,
3-thiol group butyl (dodecyloxy) tetradecyloxyaniline (n-Hexadecane oxygen base) silane,
3-thiol group-2-methyl-propyl (Trimethoxy silane),
3-thiol group-2-methyl-propyl (triethoxyl silane),
3-thiol group-2-methyl-propyl (diethoxy methoxy silane),
3-thiol group-2-methyl-propyl (tripropoxy silane),
3-thiol group-2-methyl-propyl (dipropoxy methoxy silane),
3-thiol group-2-methyl-propyl (three dodecyloxy silane),
3-thiol group-2-methyl-propyl (three tetradecyloxyaniline silane),
3-thiol group-2-methyl-propyl (three n-Hexadecane TMOS),
3-thiol group-2-methyl-propyl (three octadecane TMOS),
3-thiol group-2-methyl-propyl (two dodecyloxy) tetradecyloxyaniline silane,
3-thiol group-2-methyl-propyl (dodecyloxy) tetradecyloxyaniline (n-Hexadecane oxygen base) silane,
3-thiol group-2-methyl-propyl (dimethoxy-methyl silane),
3-thiol group-2-methyl-propyl (methoxyl group dimethylsilane),
3-thiol group-2-methyl-propyl (diethoxymethyl silane),
3-thiol group-2-methyl-propyl (oxyethyl group dimethylsilane),
3-thiol group-2-methyl-propyl (hydroxyl dimethylsilane),
3-thiol group-2-methyl-propyl (dipropoxy methyl-monosilane),
3-thiol group-2-methyl-propyl (propoxy-dimethylsilane),
3-thiol group-2-methyl-propyl (diisopropoxy methyl-monosilane),
3-thiol group-2-methyl-propyl (isopropoxy dimethylsilane),
3-thiol group-2-methyl-propyl (dibutoxy methyl-monosilane),
3-thiol group-2-methyl-propyl (butoxy dimethylsilane),
3-thiol group-2-methyl-propyl (two isobutoxy methyl-monosilanes),
3-thiol group-2-methyl-propyl (isobutoxy dimethylsilane),
3-thiol group-2-methyl-propyl (two dodecyloxy methyl-monosilane),
3-thiol group-2-methyl-propyl (dodecyloxy dimethylsilane),
3-thiol group-2-methyl-propyl (two tetradecyloxyaniline methyl-monosilane) or
3-thiol group-2-methyl-propyl (tetradecyloxyaniline dimethylsilane).
[(C 9H 19O-(CH 2-CH 2O) 2](MeO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 3](MeO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 4](MeO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 5](MeO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 6](MeO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 2](MeO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 3](MeO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 4](MeO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 5](MeO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 6](MeO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 2](MeO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 3](MeO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 4](MeO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 5](MeO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 6](MeO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 2](MeO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 3](MeO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 4](MeO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 5](MeO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 6](MeO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 2] 2(MeO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 3] 2(MeO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 4] 2(MeO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 5] 2(MeO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 6] 2(MeO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 2] 2(MeO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 3] 2(MeO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 4] 2(MeO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 5] 2(MeO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 6] 2(MeO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 2] 2(MeO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 3] 2(MeO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 4] 2(MeO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 5] 2(MeO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 6] 2(MeO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 2] 2(MeO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 3] 2(MeO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 4] 2(MeO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 5] 2(MeO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 6] 2(MeO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 2](EtO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 3](EtO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 4](EtO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 5](EtO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 6](EtO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 2](EtO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 3](EtO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 4](EtO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 5](EtO) 2Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 6](EtO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 2](EtO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 3](EtO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 4](EtO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 5](EtO) 2Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 6](EtO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 2](EtO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 3](EtO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 4](EtO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 5](EtO) 2Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 6](EtO) 2Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 2] 2(EtO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 3] 2(EtO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 4] 2(EtO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 5] 2(EtO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 6] 2(EtO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 2] 2(EtO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 3] 2(EtO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 4] 2(EtO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 5] 2(EtO)Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 6] 2(EtO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 2] 2(EtO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 3] 2(EtO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 4] 2(EtO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 5] 2(EtO)Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 6] 2(EtO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 2] 2(EtO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 3] 2(EtO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 4] 2(EtO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 5] 2(EtO)Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 6] 2(EtO)Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 2] 3Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 3] 3Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 4] 3Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 5] 3Si(CH 2) 3SH、
[(C 9H 19O-(CH 2-CH 2O) 6] 3Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 2] 3Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 3] 3Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 4] 3Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 5] 3Si(CH 2) 3SH、
[(C 12H 25O-(CH 2-CH 2O) 6] 3Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 2] 3Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 3] 3Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 4] 3Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 5] 3Si(CH 2) 3SH、
[(C 13H 27O-(CH 2-CH 2O) 6] 3Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 2] 3Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 3] 3Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 4] 3Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 5] 3Si(CH 2) 3SH、
[(C 14H 29O-(CH 2-CH 2O) 6] 3Si (CH 2) 3SH or
HS-CH 2-CH 2-CH 2-Si(OCH 2-CH 2-) 3N。
The method according to this invention can be implemented under the hydrogenolysis condition.
Hydrogenization can be implemented under the hydrogen pressure of 5 to 250 crust, is preferably 10 to 200 crust, is preferably 10 to 99 crust especially, most preferably is 10 to 75 crust, overvoltage.
Hydrogenization can be implemented under 50 to 250 ℃ temperature, is preferably 75 to 199 ℃, is preferably 100 to 175 ℃ especially, most preferably is 110 to 170 ℃.
The reaction times of hydrogenization can be preferably less than 270 minutes less than 300 minutes, was preferably especially less than 240 minutes, most preferably was less than 210 minutes.
Before reaction, during or when finishing, can in reaction mixture, add additive.
This additive can prolong the work-ing life of catalyst system therefor.This additive can make the simpler or use with improvement of catalyst system therefor.This additive can improve the reusability of catalyst system therefor.This additive can improve the economy of this method.
Additive can be organosulfur compound, alkoxylate titanium, amine, organic acid or mineral acid, organic bases or mineral alkali, or its mixture.
Additive can be carboxylic acid, DMSO, monoalkylamine, two alkylamine or trialkylamine.Additive can be Ti (OC 4H 9) 4Or Ti (OC 3H 7) 4
Catalyzer can be transition-metal catalyst, and its catalytic active component comprises the metal of one or more kind group VIIIs.Catalytic active component can use nickel, cobalt, rhodium, ruthenium, palladium, iridium or platinum.
Can additionally mix catalytic active component, or this catalytic active component can comprise extra composition, for example basic metal is preferably Li, Na, K or Rb; Alkaline-earth metal is preferably Be, Mg, Ca, Sr or Ba; The III main group element is preferably B, Al, Ga or In; The IV main group element is preferably C, Si, Ge, Sn or Pb; The V main group element is preferably N, P, As or Sb; The VI main group element is preferably O, S, Se or Te; The VII main group element is preferably F, Cl, Br or I; Or subgroup element, be preferably 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.
Preferably mix composition and can be hydride, oxide compound, halogenide, for example fluorochemical, muriate, bromide or iodide, sulfide or nitride.
The transition-metal catalyst that mixes can be and mixes such as the transition metal of molybdenum and/or the Raney type stephanoporate framework catalyzer of transistion metal compound.
The transition-metal catalyst that mixes can be and mixes such as the transition metal of molybdenum and/or the Raney type porous activated metal catalyzer of transistion metal compound.The transition-metal catalyst that mixes preferably can be and has mixed such as the transition metal of molybdenum and/or the Raney type activated ni metal catalyst of transistion metal compound.
Weight based on the transition-metal catalyst that mixes, the part by weight that mixes composition (element state or as chemical compound) can be 0.00001 to 80 weight %, more preferably 0.0001 to 50 weight % is preferably 0.001 to 15 weight % especially, most preferably is 0.01 to 7.5 weight %.
Catalytic active component can be made up of the activated metal of fine dispersion, not carrying.Can use that this is activated, metal of not carrying is as in the suspensoid or embed solid matter in wax or the oil.
Catalytic active component can be coated on the catalyst support material known or commonly used, for example diatomaceous soil, carbon, silicon-dioxide, gac, diatomite, alumina or pure aluminium silicate.
Based on catalytically-active metals, catalyst concn can be two (alkoxysilyl organic radical) polysulphides of per 1 gram of 0.0001 to 1 mmole.
Preferably cobalt is as reactive metal, and based on catalytically-active metals, catalyst concn is 0.001 to 1 mmole, and more preferably 0.008 to 0.5 mmole most preferably is two (alkoxysilyl organic radical) polysulphides of per 1 gram of 0.01 to 0.1 mmole.
Preferably nickel is as reactive metal, and based on catalytically-active metals, catalyst concn is 0.001 to 1 mmole, and more preferably 0.01 to 1 mmole most preferably is two (alkoxysilyl organic radical) polysulphides of per 1 gram of 0.1 to 0.9 mmole.
Preferably ruthenium is as reactive metal, and based on catalytically-active metals, catalyst concn is 0.001 to 1 mmole, and more preferably 0.005 to 0.5 mmole most preferably is two (alkoxysilyl organic radical) polysulphides of per 1 gram of 0.005 to 0.1 mmole.
Preferably rhodium is as reactive metal, and based on catalytically-active metals, catalyst concn is 0.001 to 1 mmole, and more preferably 0.005 to 0.5 mmole most preferably is two (alkoxysilyl organic radical) polysulphides of per 1 gram of 0.005 to 0.1 mmole.
Preferably palladium is as reactive metal, and based on catalytically-active metals, catalyst concn is 0.001 to 1 mmole, and more preferably 0.005 to 1 mmole most preferably is two (alkoxysilyl organic radical) polysulphides of per 1 gram of 0.05 to 1 mmole.
Preferably iridium is as reactive metal, and based on catalytically-active metals, catalyst concn is 0.001 to 1 mmole, and more preferably 0.005 to 0.5 mmole most preferably is two (alkoxysilyl organic radical) polysulphides of per 1 gram of 0.005 to 0.1 mmole.
Preferably platinum is as reactive metal, and based on catalytically-active metals, catalyst concn is 0.001 to 1 mmole, and more preferably 0.005 to 0.5 mmole most preferably is two (alkoxysilyl organic radical) polysulphides of per 1 gram of 0.005 to 0.1 mmole.
Can use by " transformation efficiency of reactant " whenever " mmole catalyst metal " whenever " minute " the transformation efficiency that concerns quantitative expression, the parameter of the hydrogenolysis speed under given temperature T and constant pressure p as a comparison.
If under lower temperature, this transformation efficiency can raise, then aspect ecological, energy aspect and economics aspect obtain significant improvement.Under the temperature that reduces, the energy benefit of this method rises, and transformation efficiency makes the space-time productive rate with rising, even under temperature that reduces or pressure, also operates the used material and the material of gained usually simplifiedly.Under lower temperature and pressure, the load of technical equipment descends.
This transformation efficiency can be two per 1 mmole catalytically-active metals per minutes of (alkoxysilyl organic radical) polysulphide of 0.001 to 10 gram.
Preferably cobalt is as reactive metal, and this transformation efficiency is 0.001 to 10 gram, is preferably 0.01 to 10 gram, is preferably two per 1 mmole catalytically-active metals per minutes of (alkoxysilyl organic radical) polysulphide of 0.1 to 5 gram especially.
Preferably nickel is as reactive metal, and this transformation efficiency is 0.001 to 10 gram, is preferably 0.01 to 10 gram, is preferably two per 1 mmole catalytically-active metals per minutes of (alkoxysilyl organic radical) polysulphide of 0.1 to 5 gram especially.
Preferably ruthenium is as reactive metal, and this transformation efficiency is 0.001 to 10 gram, is preferably 0.01 to 5 gram, is preferably two per 1 mmole catalytically-active metals per minutes of (alkoxysilyl organic radical) polysulphide of 0.1 to 3 gram especially.
Preferably rhodium is as reactive metal, and this transformation efficiency is 0.001 to 10 gram, is preferably 0.01 to 5 gram, is preferably two per 1 mmole catalytically-active metals per minutes of (alkoxysilyl organic radical) polysulphide of 0.1 to 3 gram especially.
Preferably palladium is as reactive metal, and this transformation efficiency is 0.001 to 10 gram, is preferably 0.01 to 5 gram, is preferably two per 1 mmole catalytically-active metals per minutes of (alkoxysilyl organic radical) polysulphide of 0.1 to 3 gram especially.
Preferably iridium is as reactive metal, and this transformation efficiency is 0.01 to 10 gram, is preferably 0.1 to 5 gram, is preferably two per 1 mmole catalytically-active metals per minutes of (alkoxysilyl organic radical) polysulphide of 0.15 to 3 gram especially.
Preferably platinum is as reactive metal, and this transformation efficiency is 0.01 to 10 gram, is preferably 0.1 to 5 gram, is preferably two per 1 mmole catalytically-active metals per minutes of (alkoxysilyl organic radical) polysulphide of 0.5 to 5 gram especially.
Can use by " in the formed product of mmole " whenever " catalytically-active metals " whenever " minute " the molar yield that concerns quantitative expression, the parameter of the hydrogenolysis speed under given temperature T and constant pressure p as a comparison.
This molar yield can be the per 1 mmole catalytically-active metals per minute of thiol group organic radical (organoalkoxysilane) of 0.001 to 50 mmole.
The transition-metal catalyst that can preferably contain iron, nickel, cobalt, ruthenium, rhodium, platinum, iridium or palladium, this molar yield is 0.001 to 50 mmole, 0.01 to 40 mmole more preferably, be preferably 0.05 to 30 mmole especially, most preferably be the contained group VIII transition metal per minute of per 1 mmole of thiol group organic radical (organoalkoxysilane) of 0.1 to 20 mmole.
Can make more than 90 weight % by the method according to this invention, preferably more than 92 weight %, especially preferably more than 94 weight %, most preferably used two (alkoxysilyl organic radical) polysulphides more than 96 weight % are converted into thiol group organic radical (organoalkoxysilane).
Can make the relative content (mole %) of contained two (alkoxysilyl organic radical) single sulfide keep constant by the method according to this invention.
By the method according to this invention the relative content (mole %) of contained two (alkoxysilyl organic radical) single sulfide is increased.
By the method according to this invention the relative content (mole %) of contained two (alkoxysilyl organic radical) single sulfide is descended.
In the method according to the invention, the relative content of contained two (alkoxysilyl organic radical) single sulfide is preferably less than 8 weight % less than 10 weight % in the reactant, is preferably especially less than 6 weight %, most preferably is less than 4 weight %.
The method according to this invention can be batch process or continuous processing.
This batch process can be slurry (Slurry) method or suspension method, for example in stirring-type potheater or Buss reactor.
This continuous processing can be the slurry process of continuous conveying liquids and gases.
Can use the known reactor that is used for gas/liquid/solid reaction to implement this continuous processing.The typical case of fixed-bed reactor is represented as trickle bed reactor and Liquid-phase reactor, and the typical case of suspension reactor is represented as stirred vessel, bubble tower and fluidized-bed.
Advantage according to the inventive method is, compared with prior art, even do not use highly toxic H 2S or alcohol under the condition of gentleness, also can be implemented the hydrogenization of polysulphide.Do not add specific detoxifcation reagent, do not show hydrogenization is had negative impact.
By the method according to this invention, pass through H 2Can make the Decomposition of two (alkoxysilyl organic radical) polysulphides have gratifying activity with used catalyzer.
In the method according to the invention, can not use detoxifcation reagent.
Compare with the prior art of the hydrogenization of two (alkoxysilyl organic radical) polysulphides that do not have detoxifcation reagent,, can obtain the transformation efficiency of twice in fact for example for ruthenium.Compare with the polysulfanes base silane system that does not have detoxifcation reagent in the present prior art, under the mild reaction conditions of relevant temperature and pressure, can obtain higher transformation efficiency.Higher transformation efficiency not only significantly improves the space-time productive rate, but also by two (alkoxysilyl organic radical) polysulphide H 2The reaction of enforcement reductive cleavage, the feasible specific energy consumption reduction that is used to make thiol group organic radical (organoalkoxysilane).In addition, the lower energy expenditure and the reaction conditions of milder, make equipment use still less, thereby make its loss lower.When making thiol group organic radical (organoalkoxysilane), lower energy expenditure can be improved the energy balance of the course of processing, and reduces environmental pollution.
Embodiment:
To come from US 6,433,206 comparing embodiment is summarized in the table 1.Use the disulphanes base silane mixture that is not described in more detail as the polysulfanes base silane, this mixture mainly contains two (3-triethoxysilylpropyltetrasulfide) disulphide.Not about forming the report of by product.Implement product analysis with the vapor-phase chromatography that is not described in more detail.
Figure C20051010360100301
With the disulphanes base silane is main component, will be summarized in the table 2,3 and 4 according to embodiments of the invention.According to the condition in the table 2,3 and 4, in the device of a Chemscan company, make Si 266 (commercial prod of Degussa stock company/[two (alkoxysilyl organic radical) disulphide]) catalytic hydrogenation, this device is made up of 8 parallel potheaters that utilize the oil bath heating, its reactor volume is 20 milliliters, and the anchor shape magnetic stirrer that is fixed in this reactor middle part and rotates with 1300 rev/mins frequency is housed.This stops after being reflected at the given time.
In table 2, " product composition " hurdle of 3 and 4, only consider composition thiol group propyl group (triethoxyl silane), two (triethoxysilylpropyltetrasulfide) disulphide, two (triethoxysilylpropyltetrasulfide) trisulphide and two (triethoxysilylpropyltetrasulfide) tetrasulfides.Ignore two (triethoxysilylpropyltetrasulfide) single sulfide and 3-chloropropyl (triethoxyl silane).
It is to utilize that this product is formed 1H-NMR records.
Analyze in conjunction with GC/HPLC and NMR, test used Si 266 and contain
1.7 two (triethoxysilylpropyltetrasulfide) single sulfide of weight %,
Two (triethoxysilylpropyltetrasulfide) disulphide of 84 weight %,
Two (triethoxysilylpropyltetrasulfide) trisulphides of 12 weight %, and
Two (triethoxysilylpropyltetrasulfide) tetrasulfides of 1 weight %.
The mean chain length degree that records the polysulfanes mixture is about 2.14 (only considering the mean value of S2-S8).The 3-chloropropyl (triethoxyl silane) that contains 0.8 weight % among the used Si 266.
Figure C20051010360100321
Figure C20051010360100341
With four sulfane base silanes is main component, will be summarized in the table 5 according to embodiments of the invention.According to the condition in the table 5, in the device of a Chemscan company, make Si 69 (commercial prod of Degussa stock company/[two (alkoxysilyl organic radical) tetrasulfide]) catalytic hydrogenation, this device is made up of 8 parallel potheaters that utilize the oil bath heating, its reactor volume is 20 milliliters, and the anchor shape magnetic stirrer that is fixed in this reactor middle part and rotates with 1300 rev/mins frequency is housed.This stops after being reflected at the given time.
In " product composition " hurdle of table 5, only consider composition thiol group propyl group (triethoxyl silane), two (triethoxysilylpropyltetrasulfide) disulphide, two (triethoxysilylpropyltetrasulfide) trisulphide and two (triethoxysilylpropyltetrasulfide) tetrasulfide.Ignore two (triethoxysilylpropyltetrasulfide) single sulfide and 3-chloropropyl (triethoxyl silane).
It is to utilize that the product that provides is formed 1H-NMR records.
Analyze in conjunction with GC/HPLC and NMR, test used Si 69 and contain
0.1 two (triethoxysilylpropyltetrasulfide) single sulfide of weight %,
Two (triethoxysilylpropyltetrasulfide) disulphide of 17 weight %,
Two (triethoxysilylpropyltetrasulfide) trisulphides of 27 weight %,
Two (triethoxysilylpropyltetrasulfide) tetrasulfides of 25 weight %, and
Two (triethoxysilylpropyltetrasulfide) polysulphides of about 29 weight %, wherein-S x-x 〉=5.
The mean chain length degree that records the polysulfanes mixture is about 3.75.The 3-chloropropyl (triethoxyl silane) that contains 1.4 weight % among the used Si 69.
Figure C20051010360100361
The abbreviation that is comprised in each table:
SH represents 3-thiol group propyl group (triethoxyl silane),
Two (triethoxysilylpropyltetrasulfide) disulphide of S2 representative,
Two (triethoxysilylpropyltetrasulfide) trisulphides of S3 representative,
Two (triethoxysilylpropyltetrasulfide) tetrasulfides of S4 representative.
Two (alkoxysilyl organic radical) tetrasulfides of Si 69[] and two (alkoxysilyl organic radical) disulphide of Si 266[] be commercially available two (alkoxysilyl organic radical) polysulphides of Degussa stock company.
The catalyzer of being abbreviated as H 10 5BA/W 5%Ru, E 105 RS/W 5%Pd, CE 105 R/W 5%Pd+0.5%Mo and E 105 Y/W 5% Pd is the noble metal powder catalyzer, and it is to make by a kind of precious metal composition such as ruthenium or palladium being coated in porous and having on the loading material of high surface area.In the case, based on the dry mass of this catalyzer, the content of precious metal composition is 5 weight %.These catalyzer use as Powdered, flowable solid matter.Described catalyzer is carried by gac.
The catalyzer of being abbreviated as B 111 W is the activated metal catalyzer, and it is to make by the suspension effect of elemental nickel in the aqueous solution of fine dispersion.After the metal ingredient that separates as powdered solid substance, use this catalyzer.
Catalyzer with following abbreviation contains the reactive metal of following content: H 105 BA/W 5%Ru, E 105 RS/W 5% Pd, CE 105 R/W 5% Pd+0.5% Mo, E 105 Y/W, 5% Pd and B 111 W 100% Ni.Catalyzer G-96B and T 8027 are the commercial prod of S ü d-Chemie stock company.Catalyzer G-96B contains 66% nickel and basic-type accelerator.
Catalyzer T 8027 contains 52% nickel and 2.4% zirconium.
In addition, according to rule well-known to those skilled in the art and working specification, the DRX 500 NMR devices of Bruker company are used for the analysis of product. 29The quality frequency of Si-nuclear is 99.35MHz, 1H-nuclear is 500.13MHz.With tetramethylsilane (TMS) as benchmark.
The available GC of analysis, HPLC and the NMR of two (alkoxysilyl organic radical) polysulphide, thiol group organic radical (organoalkoxysilane) and composition thereof are implemented (U. J.M ü nzenberg, D.Luginsland, A.M ü ller, 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), and 245).
In the method according to the invention, can not use detoxifcation reagent.
Compare with the prior art of the hydrogenization of two (alkoxysilyl organic radical) polysulphides that do not have detoxifcation reagent,, can obtain the transformation efficiency of twice in fact for ruthenium.

Claims (11)

1, a kind of method in order to the thiol group organic radical (organoalkoxysilane) of making general formula (II) is characterized in that, is not adding alcohol, H in a kind of solvent 2Make two (alkoxysilyl organic radical) polysulphides of general formula (I) carry out hydrogenation with hydrogen and transition-metal catalyst under the situation of S or water,
Z-A-S x-A-Z (I)，
Z-A-SH (II)，
Wherein,
X is 1 to 14 number,
Z is identical or different, and is SiX 1X 2X 3Or Si (OCH 2-CH 2-) 3N, and
X 1, X 2, X 3All can be mutually irrelevantly representation hydroxy is (OH),
Straight chain type, branching type or cyclic hydrocarbon chain with 1 to 18 carbon atom (C1-C18),
Alkyl acid substituting group (C yH 2y+1)-C (=O) O-, y=1～25 wherein,
Thiazolinyl acid substituting group, alkyl acid substituting group that is substituted or thiazolinyl acid substituting group,
Cycloalkyl with 5 to 12 carbon atoms,
Phenmethyl, the phenyl that halogen replaces or alkyl replaces,
C with straight chain type or branching type hydrocarbon chain 1-C 24Alkoxyl group,
Has C 5-C 12The cycloalkyloxy of atom,
The phenoxy group that halogen replaces or alkyl replaces,
Benzyloxy,
Alkylether radicals O-(CR I 2-CR I 2)-O-Alk, or
Alkyl, polyether base O-(CR I 2-CR I 2O) a-Alk, a=2～25 wherein, R IIrrelevantly represent H or alkyl mutually, Alk is for having 1 to 30 carbon atom (C1-C30), straight chain type or branching type, saturated alkyl chain;
A is two valency C1-C30 hydrocarbon chains of straight chain type or branching type, saturated or unsaturated, aliphatic, aromatics or aliphatic series/aromatics mixed type,
Use the combination of all non-alcohol compounds, ion type liquid or ion type liquid or mixture as described solvent, and described catalyzer comprise nickel, cobalt, rhodium, ruthenium, palladium, iridium or platinum as catalytic active component.
2, according to claim 1 in order to make the method for thiol group organic radical (organoalkoxysilane), it is characterized in that this pair (alkoxysilyl organic radical) polysulphide is the mixture of general formula (I) compound.
3, according to claim 1ly it is characterized in that this treats that two (alkoxysilyl organic radical) polysulphides of hydrogenant and polarity or nonpolar, proton type or non-proton type material mixes in order to make the method for thiol group organic radical (organoalkoxysilane).
4, the method in order to manufacturing thiol group organic radical (organoalkoxysilane) according to claim 1 is characterized in that, implements this hydrogenization under the pressure of 10 to 250 crust.
5, the method in order to manufacturing thiol group organic radical (organoalkoxysilane) according to claim 1 is characterized in that, implements this hydrogenization under 50 to 250 ℃ temperature.
6, according to claim 1ly it is characterized in that this catalytic active component is additionally mixed or contains extra composition in order to make the method for thiol group organic radical (organoalkoxysilane).
7, according to claim 6 in order to make the method for thiol group organic radical (organoalkoxysilane), it is characterized in that this catalytic active component comprises one or more kind basic metal, alkaline-earth metal, III main group element, IV main group element, V main group element, VI main group element, VII main group element or subgroup element.
8, the method in order to manufacturing thiol group organic radical (organoalkoxysilane) according to claim 1 is characterized in that, based on catalytically-active metals, this catalyst concn is two (alkoxysilyl organic radical) polysulphides of per 1 gram of 0.0001 to 1 mmole.
9, the method in order to manufacturing thiol group organic radical (organoalkoxysilane) according to claim 1 is characterized in that, implements this method in batches.
10, the method in order to manufacturing thiol group organic radical (organoalkoxysilane) according to claim 1 is characterized in that, implements this method continuously.
11, according to claim 1 in order to make the method for thiol group organic radical (organoalkoxysilane), it is characterized in that this reaction mixture contains additive.
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