CN101228209A - Process for synthesis of diorganosilanes by disproportionation of hydridosiloxanes - Google Patents

Process for synthesis of diorganosilanes by disproportionation of hydridosiloxanes Download PDF

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CN101228209A
CN101228209A CNA2005800509538A CN200580050953A CN101228209A CN 101228209 A CN101228209 A CN 101228209A CN A2005800509538 A CNA2005800509538 A CN A2005800509538A CN 200580050953 A CN200580050953 A CN 200580050953A CN 101228209 A CN101228209 A CN 101228209A
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aromatic group
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斯瓦沃米尔·鲁宾斯泰因
詹姆士·安东尼·塞拉
朱利安·霍伊诺夫斯基
维托尔德·福图尼亚克
贾恩·库里亚塔
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Momentive Performance Materials Inc
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Abstract

The present invention provides a novel method for the preparation of diorganosilanes by disproportionation of a hydridosiloxanes comprising at least one terminal SiH group and at least one siloxane bond in the presence of Lewis acid catalysts. The reaction is both selective and occurs under mild conditions. The triaryl borane, tris(petafluorophenyl)borane, is especially suited for use as a catalyst in the reaction. Organic catalysts such as tris(pentafluorophenyl)borane are typically preferred owing to their greater solubility and stability in the reaction mixture, relative to inorganic Lewis acid catalysts. The product, diorganosilane may be isolated from the product mixture by conventional techniques such as distillation.

Description

The method of synthesizing two organosilanes by the disproportionation of hydride siloxane
Background technology
The present invention relates to prepare by the disproportionation of hydride siloxane (hydridosiloxane) in the presence of lewis acid catalyst the method for two organosilanes, described hydride siloxane comprises at least one SiH end group and at least one siloxane bond.The invention still further relates to as the by product of above-mentioned reaction and the oligosiloxane that generates.
Ring-opening polymerization and polycondensation that two kinds of methods that are generally used for synthetic siloxane oligomer and polymkeric substance are cyclosiloxane.Polycondensation between functional silane or oligosiloxane causes forming siloxane bond and eliminates low-molecular-weight by product.The polycondensation of low-molecular-weight siloxane alcohol oil (siloxanol oil) is the most popular method that is used for synthetic polysiloxane, and this method generates water as by product.Also can use other non-hydrolysis-condensation reaction, described reaction causes forming different by product (referring to for example U.S. Patent application US2004/0127668A1).Major part in these condensation reactions needs the existence of catalyzer.Reported that recently organoboron compound is the extremely effectively catalyzer (WO01/74938) that reacts between hydrosilanes (hydrosilane) and the silanol, described reaction generates by product hydrogen.
Hydrosilanes and organoboron compound also are the good reductive agents of well-known aldehyde, ketone, ester, imines and other functional group.These systems also can be gone back carbinol in two-step reaction.At first, the silylanizing that alcohol takes place causes forming organoalkoxysilane, and the organoalkoxysilane division forms hydrocarbon and sily oxide in second step.Exist lewis acid catalyst (as B (C 6F 5) 3) down by silyl hydride (silyl hydride) cracking SiOC key, in many cases quantitatively and very fast generation, make it can be used for synthetic polysiloxane (US2004/0127668 A1).This method of preparation polysiloxane may be very attractive, often is that can be commercially available, cheap and easy processing because contain the matrix of SiOR and SiH group.The by product of this condensation reaction is a hydrocarbon, should the very fast generation of reaction under the condition of gentleness.
Two organosilane R 1R 2SiH 2Typically by existing under the strong reductant reduction dichlorosilane to make, costing an arm and a leg of described strong reductant, and it is abnormally dangerous when handling, these compounds can be used in electronic material, semi-conductor, the unicircuit, and are the useful intermediates that is used to prepare novel silicone and organosiloxane copolymer and small molecules (for example sila hydrocarbon (silahydrocarbon)).Dimethylsilane (Me 2SiH 2) and trimethyl silane (Me 3SiH) also be to use the chemical vapor deposition (CVD) technology to prepare the important matrix of low-K dielectric coating.Therefore, wish very much the method obtain under safety and convenience, producing as required two organosilanes.
The present invention briefly describes
The invention provides and a kind ofly contain the facilitated method that the siloxanes of at least one SiH key is produced two organosilanes by disproportionation.Exist under the lewis acid catalyst, the siloxanes that contains the SiH key carries out disproportionation reaction, and this disproportionation reaction causes hydrogen and the siloxane bond on the Siliciumatom to exchange.The final product mixtures that generates the siloxanes that comprises two organosilanes and higher molecular weight of this random method.
In one embodiment, the present invention relates to prepare the method for two organosilanes, this method is by in reaction mixture the lewis acid catalyst of significant quantity being contacted with the hydride siloxane that comprises at least one SiH end group and at least one siloxane bond, so that the product mixtures that comprises at least a two organosilanes and at least a oligosiloxane to be provided.
In another embodiment, the present invention relates to prepare the method for dialkyl silane, described method is included in the B (C that makes significant quantity in the reaction mixture 6F 5) 3The step that contacts with hydride siloxane, described hydride siloxane comprise SiH end group and at least one siloxane bond that at least one dialkyl group replaces.
In another embodiment, the present invention relates to prepare the method for dimethylsilane, described method is included in the B (C that makes significant quantity in the reaction mixture 6F 5) 3The step that catalyzer contacts with hydride siloxane, described hydride siloxane comprise SiH end group and at least one siloxane bond that at least one dimethyl replaces.
With reference to the following description and the appended claims book, various other feature, aspect and advantages of the present invention will be clearer.
Detailed description of the present invention
In following specification sheets and claims following closely, will be with reference to many terms, they should be defined as has following implication.
Singulative comprises a plurality of objects that refer to, unless this paper offers some clarification in addition.
Term as used herein " aliphatic group " is meant univalent organic group at least, and it is made up of straight or branched and acyclic atomic arrangement.Aliphatic group is defined as comprising at least one carbon atom.The atomic arrangement that comprises aliphatic group can comprise heteroatoms, and for example nitrogen, sulphur, silicon, selenium and oxygen perhaps can only be made up of carbon and hydrogen.For convenience; term " aliphatic group " is defined as comprising various functional groups herein; promptly as the part of " straight or branched and acyclic atomic arrangement "; for example alkyl, thiazolinyl, alkynyl, haloalkyl, conjugated diene, alcohol radical, ether, aldehyde radical, ketone group, carboxylic acid group, acyl group (for example, carboxylic acid derivative such as ester and acid amides), amino, nitro etc.For example 4-methylpent-1-base is the C that comprises methyl 6Aliphatic group, methyl are alkyl functional groups.Similarly, 4-nitro fourth-1-base is the C that comprises nitro 4Aliphatic group, nitro are functional groups.Aliphatic group can be the haloalkyl that comprises one or more halogen atoms, and described halogen atom can be identical or different.Halogen atom comprises for example fluorine, chlorine, bromine and iodine.The aliphatic group that comprises one or more halogen atoms comprises alkyl halide: and trifluoromethyl, bromine difluoro methyl, chlorodifluoramethyl-, hexafluoro isopropylidene, chloromethyl, difluorovinylidene, trichloromethyl, bromine dichloromethyl, brooethyl, 2-bromine trimethylene (for example-CH 2CHBrCH 2-) etc.The other example of aliphatic group comprise allyl group, aminocarbonyl (promptly-CONH 2), carbonyl, 2,2-dicyano isopropylidene (promptly-CH 2C (CN) 2CH 2-), methyl (promptly-CH 3), methylene radical (promptly-CH 2-), ethyl, ethylidene, formyl radical (promptly-CHO), hexyl, hexa-methylene, methylol (promptly-CH 2OH), mercapto methyl (promptly-CH 2SH), methylthio group (promptly-SCH 3), methylthiomethyl (promptly-CH 2SCH 3), methoxyl group, methoxycarbonyl (be CH 3OCO-), the nitro methyl (promptly-CH 2NO 2), thiocarbonyl group, trimethyl silyl (i.e. (CH 3) 3Si-), t-butyldimethylsilyl, 3-trimethoxy-silylpropyl (i.e. (CH 3O) 3SiCH 2CH 2CH 2-), vinyl, vinylidene etc.By further example, C 1-C 10Aliphatic group contains at least one but is no more than 10 carbon atoms.Methyl (promptly-CH 3) be C 1The example of aliphatic group.Decyl (is CH 3(CH 2) 9-) be C 10The example of aliphatic group.
As used herein, term " aromatic group " is meant the atomic arrangement that has monovalence at least and comprise at least one aromatic base.Have at least monovalence and comprise that the atomic arrangement of at least one aromatic base can comprise heteroatoms, for example nitrogen, sulphur, selenium, silicon and oxygen perhaps can only be made up of carbon and hydrogen.As used herein, term " aromatic group " includes but not limited to phenyl, pyridyl, furyl, thienyl, naphthyl, phenylene and xenyl.Just as mentioned, aromatic group contains at least one aromatic base.Aromatic base always has the ring texture of 4n+2 " delocalization " electronics, wherein " n " equals 1 or bigger integer, for example phenyl (n=1), thienyl (n=1), furyl (n=1), naphthyl (n=2), azulene cyclopentacycloheptene base (azulenyl group) (n=2), anthryl (n=3) etc.Aromatic group also can comprise non-aromatic portion.For example, tolyl is the aromatic group that comprises phenyl ring (aromatic base) and methylene radical (non-aromatic portion).Similarly, the tetraline group is to comprise being fused to non-fragrance ingredient-(CH 2) 4-on aromatic base (C 6H 3) aromatic group.For convenience; term " aromatic group " is defined as comprising multiple functional group herein; for example alkyl, thiazolinyl, alkynyl, haloalkyl, halogenated aromatic base, conjugated diene, alcohol radical, ether, aldehyde radical, ketone group, carboxylic acid group, acyl group (for example, carboxylic acid derivative and as ester and acid amides), amino, nitro etc.For example, the 4-aminomethyl phenyl is the C that comprises methyl 7Aromatic group, methyl are alkyl functional groups.Similarly, the 2-nitrophenyl is the C that comprises nitro 6Aromatic group, nitro are functional groups.Aromatic group comprises the halogenated aromatic group, for example 4-trifluoromethyl, hexafluoro isopropylidene two (4-benzene-1-oxygen base) (promptly-OPhC (CF 3) 2PhO-), 4-chloromethylbenzene-1-base, 3-trifluoro vinyl-2-thienyl, 3-benzenyl trichloride-1-base (are 3-CCl 3Ph-), 4-(3-bromine third-1-yl) benzene-1-base (is 4-BrCH 2CH 2CH 2Ph-) etc.Other examples of aromatic group comprise that 4-allyloxy benzene-1-oxygen base, 4-amino-benzene-1-base (are 4-H 2NPh-), 3-aminocarboxyl benzene-1-base (is NH 2COPh-), 4-benzoyl benzene-1-base, dicyano methylene-bis (4-benzene-1-oxygen base) (promptly-OPhC (CN) 2PhO-), 3-methylbenzene-1-base, methylene-bis (4-benzene-1-oxygen base) (promptly-OPhCH 2PhO-), 2-ethylbenzene-1-base, phenyl vinyl, 3-formyl-2-thienyl, 2-hexyl-5-furyl, hexa-methylene-1,6-two (4-benzene-1-oxygen base) (promptly-OPh (CH 2) 6PhO-), 4-hydroxymethyl benzene-1-base (is 4-HOCH 2Ph-), 4 mercapto methyls benzene-1-base (is 4-HSCH 2Ph-), 4-methylthio phenyl-1-base (is 4-CH 3SPh-), 3-anisole-1-base, 2-methoxycarbonyl benzene-1-oxygen base (for example methyl salicyl), 2-nitro methylbenzene-1-base (are 2-NO 2CH 2Ph), 3-trimethyl silyl benzene-1-base, 4-t-butyldimethylsilyl benzene-1-base, 4-vinyl benzene-1-base, vinylidene two (phenyl) etc.Term " C 3-C 10Aromatic group " comprise the aromatic group that contains at least three but be no more than 10 carbon atoms.Aromatic group 1-imidazolyl (C 3H 2N 2-) expression C 3Aromatic group.Phenmethyl (C 7H 8-) expression C 7Aromatic group.
As used herein, term " alicyclic group " expression has univalent group at least, and it comprises ring-type but the atomic arrangement of non-aromatic.Just as defined here, " alicyclic group " do not comprise aromatic group." alicyclic group " can comprise one or more non-annularity parts.For example, cyclohexyl methyl (C 6H 11CH 2-) be the alicyclic group that comprises cyclohexyl (for ring-type but the atomic arrangement of non-aromatic) and methylene radical (non-annularity part).Alicyclic group can comprise heteroatoms, and for example nitrogen, sulphur, selenium, silicon and oxygen perhaps can only be made up of carbon and hydrogen.For convenience; term " alicyclic group " is defined as comprising multiple functional group herein; for example alkyl, thiazolinyl, alkynyl, haloalkyl, conjugated diene, alcohol radical, ether, aldehyde radical, ketone group, carboxylic acid group, acyl group (for example, carboxylic acid derivative such as ester and acid amides), amino, nitro etc.For example, 4-methyl ring penta-1-base is the C that comprises methyl 6Alicyclic group, methyl are alkyl functional groups.Similarly, 2-nitro ring fourth-1-base is the C that comprises nitro 4Alicyclic group, nitro are functional groups.Alicyclic group can comprise one or more identical or different halogen atoms.Halogen atom comprises, for example fluorine, chlorine, bromine, iodine.The alicyclic group that comprises one or more halogen atoms comprises 2-trifluoromethyl hexamethylene-1-base, 4-bromine difluoro methyl ring suffering-1-base, 2-chlorodifluoramethyl-hexamethylene-1-base, hexafluoro isopropylidene-2, and 2-two (hexamethylene-4-yl) (promptly-C 6H 10C (CF 3) 2C 6H 10-), 2-chloromethyl hexamethylene-1-base, 3-difluoro methylene hexamethylene-1-base, 4-trichloromethyl hexamethylene-1-oxygen base, 4-bromine dichloromethyl hexamethylene-1-sulfenyl, 2-bromotrifluoromethane ring penta-1-base, 2-bromopropyl hexamethylene-1-oxygen base be (as CH 3CHBrCH 2C 6H 10-) etc.Other examples of alicyclic group comprise 4-allyloxy hexamethylene-1-base, hexamethylene-the 1-base (is H to 4-amino 2NC 6H 10-), 4-aminocarboxyl ring penta-1-base (is NH 2COC 5H 8-), 4-acetoxyl group hexamethylene-1-base, 2,2-dicyano isopropylidene two (hexamethylenes-4-oxygen base) (promptly-OC 6H 10C (CN) 2C 6H 10O-), 3-methyl cyclohexane-1-base, methylene-bis (hexamethylene-4-oxygen base) (promptly-OC 6H 10CH 2C 6H 10O-), 1-ethyl ring fourth-1-base, cyclopropyl vinyl, 3-formyl-2-tetrahydrofuran (THF), 2-hexyl-5-tetrahydrofuran (THF), hexa-methylene-1,6-two (hexamethylene 4-oxygen base) (promptly-OC 6H 10(CH 2) 6C 6H 10O-), 4-hydroxymethyl hexamethylene-1-base (is 4-HOCH 2C 6H 10-), 4-mercapto methyl hexamethylene-1-base (is 4-HSCH- 2C 6H 10-), 4-methylthio group hexamethylene-1-base (is 4-CH 3SC 6H 10-), 4-methoxyl group hexamethylene-1-base, 2-methoxycarbonyl hexamethylene-1-oxygen base (2-CH 3OCOC 6H 10O-), 4-nitro methyl cyclohexane-1-base (is NO 2CH 2C 6H 10-), 3-trimethyl silyl hexamethylene-1-base, 2-t-butyldimethylsilyl ring penta-1-base, 4-trimethoxysilylethylgroup group hexamethylene-1-base be (as (CH 3O) 3SiCH 2CH 2C 6H 10-), 4 vinyl cyclohexene-1-base, vinylidene two (cyclohexyl) etc.Term " C 3-C 10Alicyclic group " comprise the alicyclic group that contains at least three but be no more than 10 carbon atoms.Alicyclic group 2-tetrahydrofuran (THF) (C 4H 7O-) expression C 4Alicyclic group.Cyclohexyl methyl (C 6H 11CH 2-) expression C 7Alicyclic group.
As above mentioned, the present invention relates to prepare the method for two organosilanes, said method comprising the steps of: the lewis acid catalyst of significant quantity is contacted with at least a hydride siloxane, described hydride siloxane comprises at least one SiH end group and at least one siloxane bond, so that the product mixture that comprises at least a two organosilanes and at least a oligosiloxane to be provided.
In an embodiment of the invention, the hydride siloxane raw material comprises structure (I):
Figure S2005800509538D00061
Wherein, R 1, R 2Be C in each case independently 1-C 20Aliphatic group, C 3-C 40Aromatic group or C 3-C 40Alicyclic group; Z is the oxyalkylene segment by structure (II) expression:
(II)M aM′ bD cD′ dT eT′ fQ g
Wherein, subscript a, b, c, d, e, f and g are zero or positive integer independently, and wherein M has chemical formula:
R 3 3SiO 1/2，
M ' has chemical formula:
(Y)R 4 2SiO 1/2，
D has chemical formula:
R 5 2SiO 2/2，
D ' has chemical formula:
(Y)R 6SiO 2/2，
T has chemical formula:
R 7SiO 3/2，
T ' has chemical formula:
(Y)SiO 3/2，
And Q has chemical formula:
SiO 4/2，
Wherein, R 3, R 4, R 5, R 6And R 7Be C in each case independently 1-C 20Aliphatic group, C 3-C 40Aromatic group or C 3-C 40Alicyclic group; Y represents hydrogen.
In an embodiment of the invention, subscript a, b, c, d, e, f and the g of structure (II) are the number in 0～about 1000 scopes independently.In another embodiment of the present invention, subscript a, b, c, d, e, f and the g of structure (II) is the number in 0～about 500 scopes independently.In another embodiment of the present invention, subscript a, b, c, d, e, f and the g of structure (II) is the number in 0～about 100 scopes independently.Therefore, by way of example, in an embodiment of the invention, structure I I is polysiloxane part Me 3SiO (SiMe 2O) 500-, described polysiloxane partly has about 500 mean chain length, and described polysiloxane partly comprises the end group trimethyl silyl.The polysiloxane part Me of previous example 3SiO (SiMe 2O) 500-represent that by structure I I wherein subscript " a " is 1, " b " is 0, and " c " is 500, and " d " is 0, and " e " is 0, and " f " is 0, and " g " is 0, R 3And R 5Be methyl (Me).
Product two organosilanes have structure (III):
Figure S2005800509538D00081
Wherein, R 1And R 2Be C in each case independently 1-C 20Aliphatic group, C 3-C 40Aromatic group or C 3-C 40Alicyclic group.Usually, R 1, R 2, R 3, R 4, R 5, R 6And R 7Include but not limited to methyl, ethyl, n-propyl, sec.-propyl, butyl, amyl group, hexyl, octyl group, decyl, dodecyl, 1,1,1-trifluoro propyl, phenyl, naphthyl, phenmethyl, cyclohexyl, methylcyclohexyl etc.
Just as mentioned, method of the present invention need be used appropriate catalyst.In one embodiment, described catalyzer is a lewis acid catalyst.Preferred lewis acid catalyst comprises inorganic lewis acid catalyzer, for example FeCl 3, AlCl 3, ZnCl 2, ZnBr 2, BF 3Deng.The ability of any specific Louis acid catalysis novel reaction of the present invention will be the sterically hindered and Lewis acid of strength of acid, described acid and matrix and the function of the solubleness of matrix in reaction medium.Usually, inorganic Lewis acid FeCl for example 3, AlCl 3, ZnCl 2, ZnBr 2, BF 3Deng only being dissolved on a small quantity in the silicone compositions that carries out described reaction.This low catalyst solubleness tends to hinder the ability of the inorganic required reaction of lewis acid catalyst catalysis.Lewis acid catalyst with bigger solubleness in the siloxanes medium is preferred.Therefore, on the one hand, the present invention uses at least a organic lewis acid catalyst with chemical formula (IV):
(IV)MR 8 xX y
Wherein, M is selected from B, Al, Ga, In and Tl, each R 8For having the aromatic group of 5～14 carbon atoms, wherein X is a halogen atom independently, and x is 1,2 or 3; Y is 0,1 or 2; Its condition is x+y=3, and further condition is that described catalyzer comprises at least one electron-withdrawing group.Suitable electron-withdrawing group comprise halogen atom ,-CF 3Group ,-NO 2Group and-the CN group.Described at least one electron-withdrawing group can be to form R 8The functional group of part, perhaps electron-withdrawing group can be directly connected on the group M, as the situation when Y is 1 or 2.In one embodiment, described catalyzer comprises at least one R 8Group, this R 8Group is the aromatic group with 5～14 carbon atoms, described radicals R 8Replaced by at least two halogen atoms.
In another embodiment, described catalyzer comprises organic Lewis acid of at least a chemical formula V:
(V)BR 8 xX y
Wherein, each R 8Independently for having the aromatic group of 5～14 carbon atoms; X is a halogen atom, and x is 1,2 or 3; Y is 0,1 or 2; Its condition is x+y=3, and further condition is that described catalyzer comprises at least one electron-withdrawing group.Suitable electron-withdrawing group comprise halogen atom ,-CF 3Group ,-NO 2Group and-the CN group.Described at least one electron-withdrawing group can be to form R 8The functional group of part, perhaps electron-withdrawing group can be directly connected on the boryl, as the situation when Y is 1 or 2 (referring to for example chemical formula XII, XIII, XVI and XVII).In one embodiment, described catalyzer comprises at least one R 8Group, this R 8Group is the aromatic group with 5～14 carbon atoms, described radicals R 8Replaced by at least two halogen atoms.In one embodiment, each radicals R 8Be the phenyl that replaces, X is halogen (referring to for example following chemical formula XVI and XVII).The exemplary of this organic lewis acid catalyst of being represented by chemical formula V includes, but are not limited to:
Figure S2005800509538D00101
(X) (C 6F 4)(C 6F 5) 2B
(XI) (C 6F 4) 3B
(XII) (C 6F 5)BF 2
(XIII) BF(C 6F 5) 2
(XIV) B(C 6F 5) 3
(XV) B(C 6H 5)(C 6F 5) 2
(XVI) BCl 2(C 6H 5)
(XVII) BCl(C 6H 5) 2
(XVIII) [C 6H 4(m-CF 3)] 3B
(XIX) [C 6H 4(p-CF 3)] 3B
(XX) [C 6H 2-2，4，6-(CF 3) 3] 3B
(XXI) [C 6H 2-3，4，5-(CF 3) 3] 3B
Wherein, in structure (X) with (XI), four fluorine atoms can be 2,3,4,5, are substituted on arbitrary position of 6-, and remaining carbon valency is replaced by hydrogen.
In one embodiment, the present invention relates to prepare the method for dialkyl silane, described method comprises step: the B (C that makes significant quantity in reaction mixture 6F 5) 3Contact with the hydride siloxane that comprises structure (XXII),
Figure S2005800509538D00121
So that the product mixtures that comprises at least a dialkyl silane and at least a oligosiloxane, wherein R to be provided 9And R 10Be C in each case independently 1-C 10Alkyl, Z are the siloxanes by structure (II) expression.In this embodiment, the product dialkyl silane has structure (XXIII):
Wherein, R 9And R 10Be univalent C in each case independently 1-C 10Alkyl.
In another embodiment, the present invention relates to prepare the method for dimethylsilane, described method is included in the B (C that makes significant quantity in the reaction mixture 6F 5) 3The step that catalyzer contacts with the hydride siloxane that comprises structure (XXIV),
Figure S2005800509538D00123
Wherein Z is the siloxanes by structure (II) expression.
The common usage quantity of described catalyzer is as follows: based on the gross weight of reaction mixture, in about 1～about 50000ppm scope; More preferably, based on the gross weight of reaction mixture, in about 10ppm～about 10000ppm scope; Most preferably, based on the gross weight of reaction mixture, in about 50ppm～about 5000ppm scope.
Described reaction can be carried out existing under the condition of solvent.Perhaps, described reaction can be carried out under the condition of solvent not having.Described solvent can be single solvent or solvent mixture.Described solvent is given the ability that strengthens control reaction mixture viscosity and speed of reaction, and the convenient means of this method exothermicity of control further is provided.Preferred solvent comprises aliphatic hydrocarbon, aromatic hydrocarbons, halohydrocarbon and oligomeric ring two organo-siloxanes (it does not comprise the Si-H key).This reaction can at room temperature be carried out, and perhaps can carry out under higher temperature, and this depends on the factor of being explained, as the existence and the type of chemical structure, catalyst concentration and the solvent of reagent and catalyzer.
The physical condition of two organic silane compounds depends on such as the substituent characteristic on the Siliciumatom, temperature, pressure and other main factor such as reaction conditions.If desired, by standard method well-known to those skilled in the art (for example distillation), this product of can emanating and purify.The method of collecting and store two organosilane products is well-known to those skilled in the art, and can be used for method of the present invention.Two organic silane compounds described herein can be used in electronic material, semi-conductor, the unicircuit, and are the useful intermediates that is used to prepare novel silicone and organosiloxane copolymer and small molecules (for example sila hydrocarbon).Two organic silane compounds also are the important matrix by the low-K dielectric coating of CVD method preparation.
Need not superfluous words, believe that those of ordinary skills by explanation described herein, can maximally utilise the present invention.Following examples provide other guidance for those of ordinary skills at enforcement inventive aspect required for protection.The embodiment that is provided only is the representativeness operation that helps the application to instruct.Therefore, these embodiment are not intended to that defined the present invention is construed as limiting to claims by any way.
Embodiment
In following examples, 1,1,3,3-tetramethyl-silica alkane is obtained by ABCR, and purifies and storage with hydrolith.1,1,3,3,5,5,7,7-prestox-1,3,5, the 7-tetrasiloxane is by Dr.
Figure S2005800509538D00131
Obtain from Lodz Technical University.By Aldrich ChemicalCo.Milwaukee, catalyzer three (pentafluorophenyl group) borine (B (C that Wisconsin obtained 6F 5) 3) under drying nitrogen, be dissolved in the toluene of pre-purification, to obtain the catalyzer liquid storage of 0.1M.Use gas-chromatography and mass spectrometry (GC/MS), analyze this reaction product.
Embodiment 11,1,3, the oligomerization of 3-tetramethyl disiloxane
In reaction flask, use the high vacuum pipeline, add 0.755 gram (g) (5.62mmol) 1,1,3, the 3-tetramethyl disiloxane and the toluene of purification in advance.Then, be full of flask, use accurate Hamilton syringe, under nitrogen gas stream, add the dodecane (the interior mark that GC analyzes) of 0.225g and the catalyzer (B (C of 0.0124g (0.024mmol) with exsiccant nitrogen 6F 5) 3).At this moment, the acute variation of observation gas.At preset time at interval, take out sample, carry out cancellation with excessive 3-ethylpyridine, and pass through gc analysis.Use the chemi-ionization technology, analyze by GC-MS and carry out signal allocation.The GC-MS analysis revealed, the primary product of this reaction is Me 2SiH 2, general formula is HMe 2Si (OSiMe 2) nOSiMe 2The oligopolymer of H, wherein n=1,2,3 ..., and (Me 2SiO) nThe cyclosiloxane of series, wherein n=3,4 and 5.
Reaction process is to be monitored by the minimizing of substrate concn, and this reaction process make good progress, and described matrix almost all transforms, and the Me that is generated 2SiH 2And HMe 2Si (OSiMe 2) nOSiMe 2H is as primary product.Compare other product, i.e. HMe with the oligopolymer of n=1 2Si (OSiMe 2) nOSiMe 2The higher oligomers of H series (n＞1) forms obviously slower.Also generate cyclic products D is arranged 3(hexamethyl cyclotrisiloxane) and D 4(octamethylcyclotetrasiloxane).The a spot of D of early stage appearance in reaction 3But, its concentration stabilize.D 4Slowly form, but its concentration stable increasing in reaction system.
Embodiment 21,1,3,3,5,5,7, the reaction of 7-prestox tetrasiloxane
In reaction flask, use the high vacuum pipeline, add 0.980 gram (g) (4.10mmol) 1,1,3,3,5,7, the 7-prestox tetrasiloxane and the toluene of purification in advance.Then, be full of flask, use accurate Hamilton syringe, flow down the dodecane (the interior mark that GC analyzes) of adding 0.225g and the catalyzer (B (C of 0.0303g (0.06mmol) at drying nitrogen with exsiccant nitrogen 6F 5) 3).At this moment, the acute variation of observation gas.Take out sample at interval at preset time, carry out cancellation, and pass through gc analysis with excessive 3-ethylpyridine.Use the chemi-ionization technology, analyze by GC-MS and carry out signal allocation.The GC-MS analysis revealed, the primary product of this reaction is Me 2SiH 2With hexamethyl cyclotrisiloxane D 3
Reaction process is to be monitored by the minimizing of substrate concn, and this reaction process demonstrates initial matrix and transforms (reducing 57% in less than 1 minute) fast, and substrate concn reduces relatively lentamente then.Primary product is D 3, its concentration increases fast, corresponding to the quick minimizing of substrate concn.Also form senior line style and cyclic oligomer, but its amount is very little.
Although the present invention is made an explanation with describe, and be not intended to be limited to given detail, because can carry out various improvement and replacement not departing from by any way under the real situation of the present invention with typical embodiment.Similarly, only use conventional test, can expect the further modification and the Equivalent of invention disclosed herein, and this modification and Equivalent are considered in the spirit and scope of the invention that claims limit for those skilled in the art.

Claims (19)

1. method for preparing two organosilanes, said method comprising the steps of: the lewis acid catalyst of significant quantity is contacted, with the hydride siloxane that comprises at least one SiH end group and at least one siloxane bond so that the product mixtures that comprises at least a two organosilanes and at least a oligosiloxane to be provided.
2. method as claimed in claim 1, wherein, described hydride siloxane comprises structure (I):
Wherein, R 1, R 2Be C in each case independently 1-C 20Aliphatic group, C 3-C 40Aromatic group or C 3-C 40Alicyclic group; Z is the siloxanes by structure (II) expression:
(II)M aM′ bD cD′ dT eT′ fQ g
Wherein, subscript a, b, c, d, e, f and g are zero or positive integer, wherein
M has chemical formula:
R 3 3SiO 1/2，
M ' has chemical formula:
(Y)R 4 2SiO 1/2，
D has chemical formula:
R 5 2SiO 2/2，
D ' has chemical formula:
(Y)R 6SiO 2/2，
T has chemical formula:
R 7SiO 3/2，
T ' has chemical formula:
(Y)SiO 3/2，
And Q has chemical formula:
SiO 4/2，
Wherein, R 3, R 4, R 5, R 6And R 7Be C in each case independently 1-C 20Aliphatic group, C 3-C 40Aromatic group or C 3-C 40Alicyclic group; Y represents hydrogen.
3. method as claimed in claim 1, wherein, described two organosilanes have following structure (III):
Figure S2005800509538C00021
Wherein, R 1And R 2Be C in each case independently 1-C 20Aliphatic group, C 3-C 40Aromatic group or C 3-C 40Alicyclic group.
4. method as claimed in claim 2, wherein, R 1, R 2, R 3, R 4, R 5, R 6And R 7In be selected from one of at least methyl, ethyl, n-propyl, sec.-propyl, butyl, amyl group, hexyl, octyl group, decyl, dodecyl, 1,1,1-trifluoro propyl, phenyl, naphthyl, phenmethyl, cyclohexyl and methylcyclohexyl.
5. method as claimed in claim 1, wherein, based on the gross weight of reaction mixture, the usage quantity scope of described catalyzer is about 1ppm～about 50000ppm by weight.
6. method as claimed in claim 1, wherein, described catalyzer has chemical formula (IV):
(IV)MR 8 xX y
Wherein, M is B, Al, Ga, In or Tl, each R 8For having the aromatic group of 5～14 carbon atoms, described catalyzer comprises at least one electron-withdrawing group independently, and X is a halogen atom, and x is 1,2 or 3, and y is 0,1 or 2, and condition is x+y=3.
7. method as claimed in claim 6, wherein, R 8Comprise at least one electrophilic part, this electrophilic partly be selected from halogen ,-CF 3,-NO 2With-CN.
8. method as claimed in claim 7, wherein, R 8Comprise at least two halogen atoms.
9. method as claimed in claim 1, wherein, described catalyzer has chemical formula V:
(V)BR 8 xX y
Wherein, each R 8Independently for having the aromatic group of 5～14 carbon atoms; Described catalyzer comprises at least one electron-withdrawing group, and X is a halogen atom, and x is 1,2 or 3, and y is 0,1 or 2, and its condition is x+y=3.
10. method as claimed in claim 9, wherein, R 8Comprise at least one electrophilic part, this electrophilic partly be selected from halogen ,-CF 3,-NO 2With-CN.
11. as the method for claim 10, wherein, R 8Comprise at least two halogen atoms.
12. method as claimed in claim 9, wherein, described catalyzer be selected from have structure (VI) to the boron compound of (XXI):
Figure S2005800509538C00041
(X) (C 6F 4)(C 6F 5) 2B
(XI) (C 6F 4) 3B
(XII) (C 6F 5)BF 2
(XIII) BF(C 6F 5) 2
(XIV) B(C 6F 5) 3
(XV) B(C 6H 5)(C 6F 5) 2
(XVI) BCl 2(C 6H 5)
(XVII) BCl(C 6H 5) 2
(XVIII) [C 6H 4(m-CF 3)] 3B
(XIX) [C 6H 4(p-CF 3)] 3B
(XX) [C 6H 2-2，4，6-(CF 3) 3] 3B
(XXI) [C 6H 2-3，4，5-(CF 3) 3] 3B
13. method as claimed in claim 9, wherein, described catalyzer is three (pentafluorophenyl group) borine.
14. method as claimed in claim 1, wherein, described reaction mixture further comprises at least a solvent.
15. method as claimed in claim 1, wherein, described contact is included under the interior temperature of about 0 ℃～about 150 ℃ of scopes heats.
16. method as claimed in claim 1, wherein, two organosilanes are separated from product mixtures by distillation.
17. a method for preparing dialkyl silane said method comprising the steps of: the B (C that in reaction mixture, makes significant quantity 6F 5) 3Contact with the hydride siloxane that comprises structure (XXII),
So that the product mixtures that comprises at least a dialkyl silane and at least a oligosiloxane, wherein R to be provided 9And R 10Be C in each case independently 1-C 10Alkyl, Z are the siloxanes by structure (II) expression:
(II)M aM′ bD cD′ dT eT′ fQ g
Wherein, subscript a, b, c, d, e, f and g are zero or positive integer, wherein
M has chemical formula:
R 3 3SiO 1/2，
M ' has chemical formula:
(Y)R 4 2SiO 1/2，
D has chemical formula:
R 5 2SiO 2/2，
D ' has chemical formula:
(Y)R 6SiO 2/2，
T has chemical formula:
R 7SiO 3/2，
T ' has chemical formula:
(Y)SiO 3/2，
And Q has chemical formula:
SiO 4/2，
Wherein, R 3, R 4, R 5, R 6And R 7Be monovalence C in each case independently 1-C 20Aliphatic group, monovalence C 3-C 40Aromatic group or monovalence C 3-C 40Alicyclic group; Y represents hydrogen.
18. as the method for claim 17, wherein, described dialkyl silane has structure (XXIII):
Figure S2005800509538C00071
Wherein, R 9And R 10Be C in each case independently 1-C 10Alkyl.
19. a method for preparing dimethylsilane said method comprising the steps of: the B (C that in reaction mixture, makes significant quantity 6F 5) 3Catalyzer contacts with the hydride siloxane that comprises structure (XXIV):
Figure S2005800509538C00072
Wherein Z is the siloxanes by structure (II) expression,
(II)M aM′ bD cD′ dT eT′ fQ g
Wherein, subscript a, b, c, d, e, f and g are zero or positive integer, wherein
M has chemical formula:
R 3 3SiO 1/2，
M ' has chemical formula:
(Y)R 4 2SiO 1/2，
D has chemical formula:
R 5 2SiO 2/2，
D ' has chemical formula:
(Y)R 6SiO 2/2，
T has chemical formula:
R 7SiO 3/2，
T ' has chemical formula:
(Y)SiO 3/2，
And Q has chemical formula:
SiO 4/2，
Wherein, R 3, R 4, R 5, R 6And R 7Be C in each case independently 1-C 20Aliphatic group, C 3-C 40Aromatic group or C 3-C 40Alicyclic group; Y represents hydrogen.
CNA2005800509538A 2005-06-30 2005-08-29 Process for synthesis of diorganosilanes by disproportionation of hydridosiloxanes Pending CN101228209A (en)

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CN108690198A (en) * 2018-05-15 2018-10-23 杭州师范大学 A kind of method that three (pentafluorophenyl group) borine catalysis prepare methyl phenyl silicone oil
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108137812A (en) * 2015-10-16 2018-06-08 信越化学工业株式会社 The manufacturing method of Silicon Containing Hydrogen alkyl organic siliconresin
CN108137812B (en) * 2015-10-16 2021-05-28 信越化学工业株式会社 Method for producing hydrosilyl-containing silicone resin
CN111527131A (en) * 2017-12-30 2020-08-11 美国圣戈班性能塑料公司 Heterochain polymer compositions
CN111527131B (en) * 2017-12-30 2022-09-27 美国圣戈班性能塑料公司 Heterochain polymer compositions
CN108690198A (en) * 2018-05-15 2018-10-23 杭州师范大学 A kind of method that three (pentafluorophenyl group) borine catalysis prepare methyl phenyl silicone oil
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