CN102875589A - Ethyl-containing organosilicon compound and preparation method thereof - Google Patents
Ethyl-containing organosilicon compound and preparation method thereof Download PDFInfo
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- CN102875589A CN102875589A CN201110194596XA CN201110194596A CN102875589A CN 102875589 A CN102875589 A CN 102875589A CN 201110194596X A CN201110194596X A CN 201110194596XA CN 201110194596 A CN201110194596 A CN 201110194596A CN 102875589 A CN102875589 A CN 102875589A
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- silicoorganic compound
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Abstract
The invention relates to an ethyl-containing organosilicon compound and a preparation method thereof. The ethyl-containing organosilicon compound is prepared from an organosilicon compound and hydrogen under the conditions of an agitation speed of 500-800 r/min, reaction time of 60-200 DEG C and reaction pressure of 0.5-10 MPa, in presence of a catalyst. The method has the advantages of environmental protection, simple process, high product yield, high purity, etc.
Description
Technical field
The present invention relates to a kind of preparation method who contains the ethyl silicoorganic compound.
Background technology
The ethyl organosilicon product has the performance that is better than the methylsiloxane product; such as ethyl silicon rubber better winter hardiness is arranged; ethyl silicon oil has better oilness; the ethyl linking agent can improve the room temperature vulcanized silicone rubber processing characteristics; improve its quality etc.; also having the hydrophobicity that is better than the methylsiloxane material, is good yarn fabric auxiliary agent and Preservation of cultural building relics material etc., and ethyl organosilicon product application prospect is very wide.
One of main preparation methods that contains ethyl chlorosilane and ethylsilane TMOS is the Grignard reagent method, because this method is used the inflammable and explosive solvents such as a large amount of ether or tetrahydrofuran (THF), ether or tetrahydrofuran (THF) good water solubility, volatility are large, reclaim difficulty, loss is large, and cost is high, this method has also been used metal magnesium powder, improper very easily the causing of heating up in process of production rushes material or blast, and in addition, this method environmental pollution is serious.CN101597303A discloses the preparation method of a kind of Hexaethyl cyclosiloxane or methylethyl cyclotrisiloxane, adopt tetraalkoxysilane or methyl trialkoxysilane and MAGNESIUM METAL, halohydrocarbons reaction to generate Grignard reagent grignard reaction occurs in solvent, a series of processes such as product hydrolysis, neutralization, cracking rearrangement are obtained Hexaethyl cyclosiloxane or methylethyl cyclotrisiloxane.
US2626268 discloses a kind of preparation method of methylethyl dichlorosilane, adopts methyl hydrogen dichlorosilane and ethene addition reaction under catalyst action and certain temperature and pressure to obtain the methylethyl dichlorosilane.
US4196319 discloses a kind of preparation method of ethyl trichlorosilane, adopts hydrogeneous trichlorosilane and ethene to react under platinum or palladium catalyst and makes ethyl trichlorosilane.
CN101735263A discloses a kind of preparation method of ethyl trimethoxy silane, adopts hydrogeneous Trimethoxy silane, ethene to make ethyl trimethoxy silane under catalyzer, promotor effect.
Above-mentioned, the catalysis additive process is substantially all utilized the hydrogen silicification reaction, and the product component is many, and cost is high.
Summary of the invention
The object of the invention is to solve above-mentioned deficiency, a kind of method of ethylated silicoorganic compound is provided.
The present invention also has the product yield height, the purity advantages of higher.
Realize that technical scheme of the present invention is: a kind of preparation method who contains the ethyl silicoorganic compound, for under catalyst action, by structural formula for the organic compound that contains vinyl of (I) and hydrogen addition reaction obtain structural formula be (II) contain the ethyl silicoorganic compound;
R
aViSiX
3-aPerhaps [RViSiO]
n(I)
Wherein, R is selected from H, CH
3X is selected from Cl, MeO, EtO; A is 0,1,2;
R
aEtSiX
3-aPerhaps [REtSiO]
n(II)
Wherein, R is selected from H, CH
3, C
2H
5X is selected from F, Cl, Br, MeO, EtO; A is 0 or 1 or 2; [REtSiO] n is cyclosiloxane or polysiloxane, and n is the integer of 3-1000.
The above-mentioned preparation method who contains the ethyl silicoorganic compound comprises the steps:
(1) with catalyzer ultra-sonic dispersion 5-30min in solvent;
Silicoorganic compound and the catalyzer that (2) will contain vinyl are put into reactor, reactor is vacuumized or lead to nitrogen;
(3) the turn on agitator rotating speed is 500-800r/min, and reactor is warming up to 60-200 ℃;
(4) add hydrogen to reactor continuously or intermittently, pressure remains on 0.5-10MPa, stirring reaction 1-8h;
(5) cool off, leave standstill, filter, distill and to get product.
The above-mentioned preparation method who contains the ethyl silicoorganic compound, the described silicoorganic compound that contain vinyl are a kind of in vinyl trichloro silane, vinyl hydrogen dichlorosilane, methyl ethylene dichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl hydrogen dimethylamino TMOS, vinyl hydrogen diethoxy silane, methyl ethylene dimethoxy silane, methyl ethylene diethoxy silane, methyl ethylene cyclotrisiloxane, methyl ethylene cyclotetrasiloxane, the methylvinyl-polysiloxane.
The above-mentioned preparation method who contains the ethyl silicoorganic compound, described catalyzer is nickel catalyst and noble metal catalyst, wherein nickel catalyst is skeleton nickel, and noble metal catalyst is a kind of in the title complex of Pd/C catalyzer, Pt/C catalyzer, Ru/C catalyzer, Platinic chloride, chlorine platinum palladium, rhodium chloride, ruthenium chloride and chlorine platinum palladium, rhodium chloride, ruthenium chloride.
The above-mentioned preparation method who contains the ethyl silicoorganic compound, described noble metal catalyst is RuCl (PPh
3)
3, RuCl
2(PPh
3)
3, RuCl
3(PPh
3)
3, PbCl (PPh
3)
3, PbCl
2(PPh
3)
3, PbCl
3(PPh
3)
3, RhCl (PPh
3)
3, RhCl
2(PPh
3)
3, RhCl
3(PPh
3)
3In a kind of.
The above-mentioned preparation method who contains the ethyl silicoorganic compound, described nickel catalyst is skeleton nickel.
The above-mentioned preparation method who contains the ethyl silicoorganic compound, when described catalyzer was nickel catalyst, the catalyzer add-on was the 1-20% that contains the quality of vinyl organosilicon compound.
The above-mentioned preparation method who contains the ethyl silicoorganic compound, when described catalyzer was noble metal catalyst, the catalyzer add-on was the 0.001-1% that contains the quality of vinyl organosilicon compound.
Reactor is warming up to 100 ℃ among the above-mentioned preparation method who contains the ethyl silicoorganic compound, step (3).
The above-mentioned preparation method who contains the ethyl silicoorganic compound, step (4) pressure remains on 2Mpa.
Beneficial effect of the present invention:
(1) environmental protection, technique are simple; (2) product yield is high, and purity is high.
Description of drawings
For content of the present invention is more likely to be clearly understood, the below according to specific embodiment and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of embodiment one raw material methyl ethylene cyclosiloxane.
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram of the product methylethyl cyclosiloxane of embodiment one.
Embodiment
Synthesizing of the ethylated silicoorganic compound of the present invention, can adopt following process to carry out:
1-20% Raney's nickel or 0.001-1% noble metal catalyst ultra-sonic dispersion 5-30min in solvent; 100 parts of silicoorganic compound and catalyzer that contain vinyl are put into reactor, and vacuum or nitrogen are removed air in the reactor; Open and stir, rotating speed 500-800r/min is warming up to 60-200 ℃; Pass into hydrogen continuously or intermittently, pressure 0.5-10MPa, reaction 1-8h; Cooling, leave standstill, filter, low-boiling point material is removed in distillation, namely gets to contain the ethyl silicoorganic compound shown in the structural formula I.
The present invention will be elaborated to concrete technical scheme of the present invention by following specific embodiment, but the present invention does not limit to embodiment proposed below.
(embodiment 1)
With 60g methyl ethylene cyclosiloxane, its nucleus magnetic hydrogen spectrum spectrogram is shown in figure one, and the Raney's nickel catalyst of 10g ultra-sonic dispersion 25min in ethanol is put into autoclave, vacuum pump is taken out the air in the reactor, opens and stirs, rotating speed 600r/min, be warming up to 100 ℃, pass into continuously hydrogen, pressure 2MPa, stirring reaction 4h, cooling is left standstill, filter, distillation gets water white transparency product methylethyl cyclosiloxane, and its nucleus magnetic hydrogen spectrum spectrogram as shown in Figure 2.
Fig. 1, Fig. 2 show that the vinyl in the methyl ethylene cyclosiloxane is converted into ethyl fully, and the raw material of all the other embodiment and product are measured through nucleus magnetic hydrogen spectrum, confirm that all the gained compound structure is correct, and the validity of method of the present invention is described.
(embodiment 2)
With the 60g vinyltriethoxysilane, the Raney's nickel catalyst of 12g ultra-sonic dispersion 15min in normal hexane is put into autoclave, and vacuum pump is taken out the air in the reactor, open and stir, rotating speed 600r/min is warming up to 80 ℃, pass into continuously hydrogen, pressure 0.5MPa, stirring reaction 1h, cooling, leave standstill, filter, distillation gets water white transparency product ethyl triethoxysilane.
(embodiment 3)
With 60g high-vinyl silicone oil (2000cs, 25 ℃), the Raney's nickel catalyst of 0.6g ultra-sonic dispersion 10min in normal hexane is put into autoclave, air in the nitrogen replacement reactor is opened and is stirred, rotating speed 800r/min, be warming up to 100 ℃, intermittently pass into hydrogen, be forced into 3Mpa, through behind the hydrogenation repeatedly, until after temperature, pressure do not change, remain on 100 ℃, 2MPa, reaction 6h, cooling is left standstill, filter, underpressure distillation gets water white transparency product methylethyl polysiloxane.
(embodiment 4)
With the 50g vinyl trichloro silane, 0.0005g Pd/C catalyzer (Pd content 15%) is put into autoclave, with the air in the nitrogen replacement reactor, open and stir, rotating speed 600r/min is warming up to 60 ℃, pass into continuously hydrogen, pressure 4MPa keeps 60 ℃, 4MPa continuation reaction 8h, cooling, filter, distill to get ethyl trichlorosilane.
(embodiment 5)
With 50g methyl ethylene dichlorosilane, 0.5g the tetrahydrofuran solution of 25mmol/L three (triphenylphosphine) rhodium chloride (I) is put into reactor, with the air in the nitrogen replacement reactor, open and stir, rotating speed 600r/min is warming up to 60 ℃, then with pressurized with hydrogen to 10MPa, keep 60 ℃, 10MPa continuation reaction 4h, cooling is filtered, and distills to get the methylethyl dichlorosilane.
Claims (10)
1. preparation method who contains the ethyl silicoorganic compound is characterized in that: under catalyst action, by structural formula for the organic compound that contains vinyl of (I) and hydrogen addition reaction obtain structural formula be (II) contain the ethyl silicoorganic compound;
R
aViSiX
3-aPerhaps [RViSiO]
n(I)
Wherein, R is selected from H, CH
3X is selected from Cl, MeO, EtO; A is 0,1,2;
R
aEtSiX
3-aPerhaps [REtSiO]
n(II)
Wherein, R is selected from H, CH
3, C
2H
5X is selected from F, Cl, Br, MeO, EtO; A is 0 or 1 or 2; [REtSiO] n is cyclosiloxane or polysiloxane, and n is the integer of 3-1000.
2. the preparation method who contains the ethyl silicoorganic compound according to claim 1 is characterized in that: comprise the steps:
(1) with catalyzer ultra-sonic dispersion 5-30min in solvent;
Silicoorganic compound and the catalyzer that (2) will contain vinyl are put into reactor, reactor is vacuumized or lead to nitrogen;
(3) the turn on agitator rotating speed is 500-800r/min, and reactor is warming up to 60-200 ℃;
(4) add hydrogen to reactor continuously or intermittently, pressure remains on 0.5-10MPa, stirring reaction 1-8h;
(5) cool off, leave standstill, filter, distill and to get product.
3. the preparation method who contains the ethyl silicoorganic compound according to claim 1 and 2, it is characterized in that: the silicoorganic compound that contain vinyl are a kind of in vinyl trichloro silane, vinyl hydrogen dichlorosilane, methyl ethylene dichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl hydrogen dimethylamino TMOS, vinyl hydrogen diethoxy silane, methyl ethylene dimethoxy silane, methyl ethylene diethoxy silane, methyl ethylene cyclotrisiloxane, methyl ethylene cyclotetrasiloxane, the methylvinyl-polysiloxane.
4. the preparation method who contains the ethyl silicoorganic compound according to claim 1 and 2, it is characterized in that: catalyzer is nickel catalyst and noble metal catalyst, wherein nickel catalyst is skeleton nickel, and noble metal catalyst is a kind of in the title complex of Pd/C catalyzer, Pt/C catalyzer, Ru/C catalyzer, Platinic chloride, chlorine platinum palladium, rhodium chloride, ruthenium chloride and chlorine platinum palladium, rhodium chloride, ruthenium chloride.
5. the preparation method who contains the ethyl silicoorganic compound according to claim 4, it is characterized in that: noble metal catalyst is RuCl (PPh
3)
3, RuCl
2(PPh
3)
3, RuCl
3(PPh
3)
3, PbCl (PPh
3)
3, PbCl
2(PPh
3)
3, PbCl
3(PPh
3)
3, RhCl (PPh
3)
3, RhCl
2(PPh
3)
3, RhCl
3(PPh
3)
3In a kind of.
6. the preparation method who contains the ethyl silicoorganic compound according to claim 4, it is characterized in that: nickel catalyst is skeleton nickel.
7. the preparation method who contains the ethyl silicoorganic compound according to claim 2, it is characterized in that: when catalyzer was nickel catalyst, the catalyzer add-on was the 1-20% that contains the quality of vinyl organosilicon compound.
8. the preparation method who contains the ethyl silicoorganic compound according to claim 2, it is characterized in that: when catalyzer was noble metal catalyst, the catalyzer add-on was the 0.001-1% that contains the quality of vinyl organosilicon compound.
9. the preparation method who contains the ethyl silicoorganic compound according to claim 2 is characterized in that: reactor is warming up to 100 ℃ in the step (3).
10. the preparation method who contains the ethyl silicoorganic compound according to claim 2, it is characterized in that: step (4) pressure remains on 2Mpa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19822252A1 (en) * | 1998-05-18 | 1999-11-25 | Wacker Chemie Gmbh | Hydrogenation of alkenyl groups in cyclo-siloxane compounds with alkenyl and alkyl groups, useful in the purification of products from silicone recycling |
| CN1642963A (en) * | 2002-03-27 | 2005-07-20 | 辛根塔参与股份公司 | Siliconated phenyl amides derivatives useful as microbiocide |
-
2011
- 2011-07-12 CN CN201110194596XA patent/CN102875589A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19822252A1 (en) * | 1998-05-18 | 1999-11-25 | Wacker Chemie Gmbh | Hydrogenation of alkenyl groups in cyclo-siloxane compounds with alkenyl and alkyl groups, useful in the purification of products from silicone recycling |
| CN1642963A (en) * | 2002-03-27 | 2005-07-20 | 辛根塔参与股份公司 | Siliconated phenyl amides derivatives useful as microbiocide |
Non-Patent Citations (4)
| Title |
|---|
| A. I. MIKAYA等,: "Selective on-line deuteration in gas chromatography-mass spectrometry for the investigation of dissociative ionization of silicon-containing compounds", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》, 26 March 1985 (1985-03-26) * |
| EWA MIECZYNSKA等,: "Hydroformylation and related reactions of vinylsilanes catalyzed by siloxide complexes of rhodium(I) and iridium(I)", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, 13 June 2005 (2005-06-13), pages 246 - 253 * |
| FRANK J. FEHER等,: "Methods for effecting monofunctionalization of (CH2=CH)8Si8O12", 《CHEM. COMMUN.》, 31 December 1999 (1999-12-31), pages 1289 - 1290 * |
| LARRY N. LEWIS: "Enhancement of Catalytic Activity through Orthometalation. Synthesis, Structure, and Catalytic Activity of a New Orthometalated Ruthenium Complex", 《J. AM. CHEM. SOC.》, 28 February 1986 (1986-02-28), pages 743 - 749, XP002236885, DOI: doi:10.1021/ja00264a028 * |
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Application publication date: 20130116 |