CN102898459B - Preparation method of diethyldimethoxysilane - Google Patents
Preparation method of diethyldimethoxysilane Download PDFInfo
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- CN102898459B CN102898459B CN201210222070.2A CN201210222070A CN102898459B CN 102898459 B CN102898459 B CN 102898459B CN 201210222070 A CN201210222070 A CN 201210222070A CN 102898459 B CN102898459 B CN 102898459B
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- monobromethane
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- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000011734 sodium Substances 0.000 claims abstract description 47
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 47
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 41
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims abstract description 32
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 15
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 15
- 229960004756 ethanol Drugs 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000004576 sand Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000001419 dependent effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 13
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 8
- -1 polypropylene Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 238000010606 normalization Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VSPRYFWDJSXQQO-UHFFFAOYSA-N C(C)[SiH](C(OC)OC)CC Chemical compound C(C)[SiH](C(OC)OC)CC VSPRYFWDJSXQQO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006621 Wurtz reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention relates to the field of organic chemistry and provides a preparation method of diethyldimethoxysilane. The preparation method solves the problem that alcoholysis method-based synthesis of diethyldimethoxysilane has defects in safety and cost. The preparation method comprises that the diethyldimethoxysilane is synthesized from ethyltrimethoxysilane and bromoethane as raw materials by a sodium condensation method. The preparation method improves reaction controllability, allows mild reaction conditions, has simple processes, realizes good selectivity of diethyldimethoxysilane in a synthesized mixture, has a high yield and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to organic chemistry filed, specifically a kind of synthetic method of the compound diethyldimethoxysilane containing element silicon.
Background technology
Diethyldimethoxysilane is a kind of important synthon, its Nature comparison is active, be used for synthesizing organo-silicon intermediate and high molecular polymer, also can be used as the constitution controller of silicon rubber, can be used as external electron donor excellent in synthesis polypropylene (PP) catalyst system in addition, improve catalyzer activity and stereoselective while, improve the over-all properties of PP.
People (Field, the Leslie D. such as Field, Leslie D; Messerle, Barbara A.; Rehr, Manuela; Soler, Linnea P.; Hambley, Trevor W. Cationic Iridium (I) Complexes as Catalysts for the Alcoholysis of Silanes. Organometallics, 2003,22 (12): 2387-2395) with diethylsilane (Et
2siH
2) and methyl alcohol as raw material, [Ir (BPM) (CO)
2]
+(BPh
4)
-as catalyzer, tetrahydrofuran (THF) (THF), as solvent, carries out alcoholysis reaction air atmosphere and 40 DEG C, obtains diethyldimethoxysilane (Et
2si (OMe)
2) content is the synthetic product of 80%.People (Nagai, the Yoichiro such as Nagai Yoichiro; Ojima, Iwao; Kogure, Tetsuo. Jpn. Kokai Tokkyo Koho, JP 1974-42615 A, 19740422) with Et
2siH
2be raw material with methyl alcohol, (Ph
3p)
3rhCl is catalyzer, reacts in ice-water bath, obtains Et
2si (OMe)
2content is the synthetic product of 99%.But adopt alcoholysis reaction technique to prepare Et
2si (OMe)
2time, not only use inflammable Et
2siH
2as raw material, and also need in reaction process to use expensive Ir or Rh metal complex as catalyzer, reaction process there is potential safety hazard and cost is higher.
Except alcoholysis reaction, prepared by sodium condensation method (Wurtz reaction) also can be used for preparing Et
2si (OMe)
2, its with ethyl trimethoxy silane and monobromethane for raw material, by generating diethyldimethoxysilane under sodium Metal 99.5 condensation.Et raw materials used with alcoholysis method
2siH
2compare, ethyl trimethoxy silane is more stable and safer; On the other hand, sodium mediated condensated reaction does not use the metals such as expensive Ir or Rh and complex compound thereof as catalyzer, has the advantage on cost.But in sodium mediated condensated reaction process, if reaction process control is improper, also may generate triethyl methoxy silane by product.The atmospheric boiling point of diethyldimethoxysilane is 130 DEG C (Emeleus, H. J. Journal of the Chemical Society 1947, P1592-1594), and the atmospheric boiling point of triethyl methoxy silane is 141 DEG C of (Mironov, I. V.; Zhurnal Obshchei Khimii 1981, V51 (12), P2700-2704), both boiling points are more close, when adopting rectificating method to carry out separating-purifying, there is certain difficulty.
Summary of the invention
For solving the problem of safety and the cost aspect faced in alcoholysis method synthesis diethyldimethoxysilane, the present invention proposes a kind of preparation method of diethyldimethoxysilane, and present method improves the controllability of reaction, and reaction conditions is gentle, and technique is simple; In synthetic mixture, the content of diethyldimethoxysilane is higher, is suitable for large-scale commercial production.
The present invention is achieved by the following technical solutions: a kind of preparation method of diethyldimethoxysilane, described diethyldimethoxysilane with ethyl trimethoxy silane and monobromethane for raw material, made by prepared by sodium condensation method, the structural formula of diethyldimethoxysilane is:
。
Reaction equation of the present invention is shown below:
A preparation method for diethyldimethoxysilane, described preparation method carries out as follows:
1) join in container by ethyl trimethoxy silane and toluene, stir and be warming up to 90 ~ 115 DEG C, as preferably, temperature is 103 ~ 115 DEG C; Under Keep agitation condition, add sodium sheet, and sodium sheet is broken into sodium sand, as preferably, the sodium sheet newly cut is broken into sodium sand under mechanical agitation;
2) monobromethane is joined in reaction system by bottom insert canal, hierarchy of control temperature is between 101 ~ 115 DEG C, monobromethane feed time is 1.0 ~ 6.0h, dropwises rear maintenance reaction mixture refluxed, continues reaction 0.1 ~ 6.0h at reflux after dropwising; As preferably, the feed time of monobromethane is 1.5 ~ 3.5h, and the continuation reaction times is 1 ~ 5h; Monobromethane is vaporized after entering reaction system by bottom insert canal at the reaction temperatures, carries out gas liquid reaction with the ethyl trimethoxy silane in liquid phase; If do not adopted dropping mode to be added drop-wise to by monobromethane in the reaction system of heat by bottom insert canal, namely the material that monobromethane one touches heat vaporizes, reaction carries out on ethyl trimethoxy silane surface, cause most of monobromethane not yet to react just to vaporize, leave reaction system in vapour form, target product diethyldimethoxysilane yield is low, and monobromethane waste is serious, and therefore monobromethane must adopt bottom insert canal to feed in raw material.
3) by step 2) reaction product that obtains is cooled to 0 ~ 50 DEG C, and as preferably, temperature is 15 ~ 40 DEG C, drips ethanol at this temperature; The consumption of the ratio-dependent ethanol of 0.1 ~ 0.2 mol ethanol is added according to every mole metal sodium; Drip dimethyldichlorosilane(DMCS) again, the consumption of the ratio-dependent dimethyldichlorosilane(DMCS) of 0.1 ~ 0.3 mol dimethyldichlorosilane(DMCS) is added according to every mole metal sodium, the time for adding of dimethyldichlorosilane(DMCS) is 0.5 ~ 4h, after dimethyldichlorosilane(DMCS) dropwises, reacts the 1 ~ 8h that holds time; As preferably, the time for adding of dimethyldichlorosilane(DMCS) is 1.5 ~ 3.5h; It is 1 ~ 6h that reaction is held time.Then employing decompress filter mode removes the solid impurity in reaction mixture, collect filtrate simultaneously, filtrate being comprises the mixing solutions of target product diethyldimethoxysilane of the present invention, adopt the separating and purifying method such as the known rectifying of chemical field or rectification under vacuum, can diethyldimethoxysilane be obtained to after the further separating-purifying of filtrate.Dripping the ethanol of some amount is to neutralize excessive sodium Metal 99.5, and after maintaining reaction certain hour, then to drip a certain amount of methyl chlorosilane be sodium alkoxide in order to neutralize generation; As preferably, ethanol is selected from dehydrated alcohol.
Described toluene consumption is 0 ~ 0.6:1 with the ratio of the amount of substance of ethyl trimethoxy silane consumption; Described ethyl trimethoxy silane consumption is 1.0 ~ 6.0:1 with the ratio of the amount of substance of monobromethane consumption, and the consumption of sodium is 1.5 ~ 2.5:1 with the ratio of the amount of substance of monobromethane consumption; As preferably, the consumption of described ethyl trimethoxy silane is 2.9 ~ 5.0:1 with the amount of substance ratio of monobromethane consumption; The consumption of sodium is 1.9 ~ 2.3:1 with the ratio of the amount of substance of monobromethane consumption; The ratio of amount of substance of the present invention is mol ratio.
The present invention is with ethyl trimethoxy silane and monobromethane for raw material, and prepare a kind of diethyldimethoxysilane by prepared by sodium condensation method, by feed change proportioning, feed time, temperature of reaction, the parameters such as solvent load, improve target product yield further.In prepared by sodium condensation method synthesis diethyldimethoxysilane, using toluene as solvent, using ethyl trimethoxy silane as reaction raw materials, sodium Metal 99.5 is dispersed in ethyl trimethoxy silane, form sodium sand, then with monobromethane generation condensation reaction, obtain the synthesis crude product containing diethyldimethoxysilane, synthesis crude product collects filtrate through known solid-liquid separating method, and filtrate is again through Liquid liquid Separation methods such as known rectifying and separablely obtain diethyldimethoxysilane.
Compared with prior art, the invention has the beneficial effects as follows:
(1) reaction conditions is gentle, and technique is simple;
(2) instant invention overcomes in conventional sodium mediated condensated reaction and generate the low shortcoming of a substitution product selectivity, by feed way and the feed rate of adjustment proportioning raw materials, monobromethane, suppress the generation of two substitution products, obtain, not containing the synthetic product of triethyl methoxy silane, improve the controllability of reaction.
(3) in synthetic mixture, the selectivity of diethyldimethoxysilane is good, and yield is higher, is very suitable for large-scale commercial production.
Embodiment
Be described in further detail the present invention below in conjunction with embodiment, but embodiment is not limiting the scope of the invention, raw material used in embodiment is commercial products.
Embodiment 1
In the dry 250mL four-hole boiling flask that reflux condensing tube, mechanical stirrer and Pt-100 RTD are housed, add 20g(0.2171 mol) toluene, 119.8g(0.7973 mol) ethyl trimethoxy silane, under agitation add 12.7g(0.5524 mol) the sodium sheet newly cut, be warming up to 109 DEG C, sodium sheet is broken into sodium sand; In 3.5h, by 29.5g(0.2707 mol) monobromethane adds in reaction system by bottom insert canal, control temperature of reaction between 107 ~ 111 DEG C, reaction 3.5h is continued at reflux after dropwising, to be cooled after 18.4 DEG C, slowly add 5.0mL(0.0857 mol) in ethanol and excessive sodium Metal 99.5; Then by 8.7g(0.0674 mol) dimethyldichlorosilane(DMCS) is added drop-wise in mixture, to neutralize the sodium alkoxide of generation in 1.5h; After dropwising, then continue reaction 3h at such a temperature.Then by reaction mixture decompress filter, mixture 98.8 g formed containing dimethyldiethoxysilane, diethyldimethoxysilane, ethyl trimethoxy silane and a small amount of polycondensation product and toluene is obtained.Filtrate adopts GC-MS to carry out analyzing (area normalization method), and diethyldimethoxysilane massfraction is 19.31%, and triethyl methoxy silane mark is 0%, and selectivity is 100%, and diethyldimethoxysilane yield is 47.53%.。
Embodiment 2
In the dry 500mL four-hole boiling flask that reflux condensing tube, mechanical stirrer and Pt-100 RTD are housed, add 20g(0.2171 mol) toluene, 159.8g(1.0636 mol) ethyl trimethoxy silane, under agitation add 12.0g(0.5220 mol) the sodium sheet newly cut, be warming up to 103 DEG C, sodium sheet is broken into sodium sand; In 2.5h, by 29.8g(0.2734mol) monobromethane adds in reaction system by bottom insert canal, control temperature of reaction between 101 ~ 105 DEG C, reaction 2.5h is continued at reflux after dropwising, to be cooled after 38 DEG C, slowly add 4.0mL(0.0685 mol) in ethanol and excessive sodium Metal 99.5; Then by 7.8g(0.0604 mol) dimethyldichlorosilane(DMCS) is added drop-wise in mixture, to neutralize the sodium alkoxide of generation in 2.5h; After dropwising, then continue reaction 2h at such a temperature.Then by reaction mixture decompress filter, the mixture 107.3g formed containing dimethyldiethoxysilane, diethyldimethoxysilane, ethyl trimethoxy silane, toluene and a small amount of polycondensation product is obtained.Filtrate adopts GC-MS to carry out analyzing (area normalization method), and diethyl dimethoxymethylsilane massfraction is 18.71%, triethyl methoxy silane 0%, and selectivity is 100%, and diethyldimethoxysilane yield is 49.50%.。
Embodiment 3
In the dry 500mL four-hole boiling flask that reflux condensing tube, mechanical stirrer and Pt-100 RTD are housed, add 199.6g(1.3285 mol) ethyl trimethoxy silane, under agitation add 12.4g(0.5394 mol) the sodium sheet newly cut, be warming up to 103 DEG C, sodium sheet is broken into sodium sand; In 2.5h, by 29.1g(0.2671 mol) monobromethane adds in reaction system by bottom insert canal, control temperature of reaction between 107 ~ 111 DEG C, reaction 5 h is continued at reflux after dropwising, to be cooled after 40 DEG C, slowly add 6.0mL(0.1028 mol) in ethanol and excessive sodium Metal 99.5; Then by 20.0g(0.1550 mol) dimethyldichlorosilane(DMCS) is added drop-wise in mixture, to neutralize the sodium alkoxide of generation in 3.5h; After dropwising, then continue reaction 1h at such a temperature.Then by reaction mixture decompress filter, the mixture 118.9g formed containing dimethyldiethoxysilane, diethyldimethoxysilane, ethyl trimethoxy silane, toluene and a small amount of polycondensation product is obtained.Filtrate adopts GC-MS to carry out analyzing (area normalization method), and diethyldimethoxysilane massfraction is 20.71%, and triethyl methoxy silane massfraction is 0%, and selectivity is 100%, and diethyldimethoxysilane yield is 62.17%.。
Embodiment 4
In the dry 500mL four-hole boiling flask that reflux condensing tube, mechanical stirrer and Pt-100 RTD are housed, add 40g(0.4341 mol) toluene, 159.8g(1.0636 mol) ethyl trimethoxy silane, under agitation add 13.0g(0.5655 mol) the sodium sheet newly cut, be warming up to 109 DEG C, sodium sheet is broken into sodium sand; In 1.5h, by 29.1g(0.2671 mol) monobromethane adds in reaction system by bottom insert canal, control temperature of reaction between 107 ~ 111 DEG C, reaction 1.5 h is continued at reflux after dropwising, to be cooled after 32.6 DEG C, slowly add 5mL(0.0857 mol) in ethanol and excessive sodium Metal 99.5; Then by 15.1g(0.1170 mol) dimethyldichlorosilane(DMCS) is added drop-wise in mixture, to neutralize the sodium alkoxide of generation in 3.0h; After dropwising, then continue reaction 4h at such a temperature.Then by reaction mixture decompress filter, obtain containing dimethyldiethoxysilane, diethyldimethoxysilane, ethyl trimethoxy silane and toluene, the mixture 120.9g that a small amount of polycondensation product forms.Filtrate adopts GC-MS to carry out analyzing (area normalization method), and diethyldimethoxysilane massfraction is 17.23%, and the massfraction of triethyl methoxy silane is 0%, and selectivity is 100%, and diethyldimethoxysilane yield is 52.60%.。
Embodiment 5
In the dry 250mL four-hole boiling flask that reflux condensing tube, mechanical stirrer and Pt-100 RTD are housed, add 40.1g(0.4352 mol) toluene, 119.7g(0.7967 mol) ethyl trimethoxy silane, under agitation add 13.5g(0.5872 mol) the sodium sheet newly cut, be warming up to 115 DEG C, sodium sheet is broken into sodium sand; In 2.5h, by 29.0g(0.2661 mol) monobromethane adds in reaction system by bottom insert canal, control temperature of reaction between 113 ~ 115 DEG C, reaction 2 h is continued at reflux after dropwising, to be cooled after 35.8 DEG C, slowly add 6.0mL(0.1028 mol) in ethanol and excessive sodium Metal 99.5; Then by 7.9g(0.0612 mol) dimethyldichlorosilane(DMCS) is added drop-wise in mixture, to neutralize the sodium alkoxide of generation in 1.5h; After dropwising, then continue reaction 6h at such a temperature.Then by reaction mixture decompress filter, obtain containing dimethyldiethoxysilane, diethyldimethoxysilane, ethyl trimethoxy silane and toluene, the mixture 112.3g that a small amount of polycondensation product forms.Filtrate adopts GC-MS to carry out analyzing (area normalization method), and diethyldimethoxysilane massfraction is 20.26%, and triethyl methoxy silane massfraction is 0%, and selectivity is 100% diethyldimethoxysilane yield is 57.66%.
Claims (7)
1. a preparation method for diethyldimethoxysilane, is characterized in that: described diethyldimethoxysilane is with ethyl trimethoxy silane and monobromethane for raw material, and made by prepared by sodium condensation method, the structural formula of diethyldimethoxysilane is:
，
The preparation method of described diethyldimethoxysilane carries out as follows:
1) ethyl trimethoxy silane and toluene are joined in container, stir and be warming up to 90 ~ 115 DEG C, under Keep agitation condition, add sodium sheet and sodium sheet is broken into sodium sand;
2) add in reaction system by monobromethane by bottom insert canal, hierarchy of control temperature is between 101 ~ 115 DEG C, and the feed time 1.0 ~ 6.0h of monobromethane, continues reaction 0.1 ~ 6.0h after dropwising at reflux;
3) by step 2) reaction product that obtains is cooled to 0 ~ 50 DEG C, drip ethanol at this temperature, and then drip dimethyldichlorosilane(DMCS), the time for adding of dimethyldichlorosilane(DMCS) is 0.5 ~ 4.0h, after dimethyldichlorosilane(DMCS) dropwises, react the 1.0 ~ 8.0h that holds time; Then employing decompress filter mode removes the solid impurity in reaction mixture, and collect filtrate, filtrate being comprises the mixing solutions of target product diethyldimethoxysilane of the present invention simultaneously;
Described toluene consumption is 0 ~ 0.6:1 with the ratio of the amount of substance of ethyl trimethoxy silane consumption; Described ethyl trimethoxy silane consumption is 1.0 ~ 6.0:1 with the ratio of the amount of substance of monobromethane consumption; The consumption of sodium is 1.5 ~ 2.5:1 with the ratio of the amount of substance of monobromethane consumption, add the consumption of the ratio-dependent ethanol of 0.1 ~ 0.2mol ethanol according to every mole metal sodium, add the consumption of the ratio-dependent dimethyldichlorosilane(DMCS) of 0.1 ~ 0.3mol chlorine atom according to every mole metal sodium.
2. the preparation method of diethyldimethoxysilane according to claim 1, is characterized in that: described ethyl trimethoxy silane consumption is 2.9 ~ 5.0:1 with the ratio of the amount of substance of monobromethane consumption; The consumption of sodium is 1.9 ~ 2.3:1 with the ratio of the amount of substance of monobromethane consumption.
3. the preparation method of diethyldimethoxysilane according to claim 1, is characterized in that: stir in step 1) and be warming up to 103 ~ 115 DEG C.
4. the preparation method of diethyldimethoxysilane according to claim 1, is characterized in that: step 2) described in the time for adding of monobromethane be 1.5 ~ 3.5h, the maintenance reaction times is 1.0 ~ 5.0h.
5. the preparation method of diethyldimethoxysilane according to claim 1, is characterized in that: at 15 ~ 45 DEG C of temperature, drip ethanol in step 3).
6. the preparation method of diethyldimethoxysilane according to claim 1 or 5, is characterized in that: ethanol is selected from dehydrated alcohol.
7. the preparation method of diethyldimethoxysilane according to claim 1, is characterized in that: the time for adding of methyl chlorosilane is 1.5 ~ 3.5h; It is 1 ~ 6h that reaction is held time.
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|---|---|---|---|
| CN201210222070.2A CN102898459B (en) | 2012-05-16 | 2012-07-02 | Preparation method of diethyldimethoxysilane |
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| CN201210222070.2A CN102898459B (en) | 2012-05-16 | 2012-07-02 | Preparation method of diethyldimethoxysilane |
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| CN102898459B true CN102898459B (en) | 2015-04-22 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500725A (en) * | 1981-07-30 | 1985-02-19 | Chisso Corporation | Silane derivative and fragrant article |
| CN1532200A (en) * | 2003-03-18 | 2004-09-29 | 武汉化工学院研究设计院 | One-step synthesizing cyclohexyl methyl dimethoxy silane without solvent |
| CN102351894A (en) * | 2011-09-22 | 2012-02-15 | 中蓝晨光化工研究设计院有限公司 | Preparation method of methylphenyldialkoxysilane |
-
2012
- 2012-07-02 CN CN201210222070.2A patent/CN102898459B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500725A (en) * | 1981-07-30 | 1985-02-19 | Chisso Corporation | Silane derivative and fragrant article |
| CN1532200A (en) * | 2003-03-18 | 2004-09-29 | 武汉化工学院研究设计院 | One-step synthesizing cyclohexyl methyl dimethoxy silane without solvent |
| CN102351894A (en) * | 2011-09-22 | 2012-02-15 | 中蓝晨光化工研究设计院有限公司 | Preparation method of methylphenyldialkoxysilane |
Non-Patent Citations (3)
| Title |
|---|
| 《Cationic Iridium(I) Complexes as Catalysts for the Alcoholysis of Silanes》;Leslie D. Field等;《Organometallics》;ACS;20030507;第22卷(第12期);第2387页方案1，第2390页表3 * |
| 《格氏法合成甲基环己基二甲氧基硅烷的研究》;张卫红等;《江苏石油化工学院学报》;CNKI;20020325;第14卷(第1期);第1-3页 * |
| 《甲基二烯丙基乙氧基硅烷的合成》;钟桂云等;《化工新型材料》;CNKI;20060730;第34卷(第7期);第71-72,80页 * |
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