CN1064867A - Direct method is synthesized organoalkoxysilane - Google Patents
Direct method is synthesized organoalkoxysilane Download PDFInfo
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- CN1064867A CN1064867A CN 92108098 CN92108098A CN1064867A CN 1064867 A CN1064867 A CN 1064867A CN 92108098 CN92108098 CN 92108098 CN 92108098 A CN92108098 A CN 92108098A CN 1064867 A CN1064867 A CN 1064867A
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Abstract
The present invention relates to the directly method of synthetic organoalkoxysilane of silicon and Fatty Alcohol(C12-C14 and C12-C18).Silica flour and copper catalyst in inert atmosphere, are handled 0.5-3h down for 200～350 ℃.Handled solid phase and suspension agent by suspension agent (volume): silica flour (weight)=1.5～3: 1 mixes, and in inert atmosphere, under 160～250 ℃, feeds the doubly straight or branched Fatty Alcohol(C12-C14 and C12-C18) of 1～4 carbon atom of (weight) of the heavy 6-10 of silica flour, reaction 3-8h.This method temperature of reaction is low, and operation is simple, and suspension agent is inexpensive, is easy to get, and consumption is few, and product yield height, silicon transformation efficiency are 85～99%, and the trialkoxy silane selectivity is 85～96%, and reaction spatiotemporal efficiency height is suitable for engineering to be amplified.
Description
The invention relates to silicon and Fatty Alcohol(C12-C14 and C12-C18) in the presence of catalyzer, directly synthetic organoalkoxysilane (HnSi(OR)
4-n, n=0,1) method.
Trialkoxy silane (n=1) is the basic raw material of synthetic coupling agent and extraordinary silane, and tetraalkoxysilane (n=0) is widely used in precision casting, the white carbon black manufacturing, binding agent, coating and special coating also can be made olefin polymerization catalysis, linking agents etc. are very important organosilicon raw materials.
Up to now, industrially prepare the method that organoalkoxysilane is still continued to use the chlorosilane alcoholysis, promptly
(R is an alkyl in the formula)
This method needs just can finish through two-step reaction, and technical process is long, and yield is low, produces a large amount of HCl during reaction, and to serious, the easy contaminate environment of equipment corrosion, and HCl reclaims trouble, and facility investment increases.
Begin one's study silicon and pure direct reaction of nineteen forty-six E.G Rochow prepares organoalkoxysilane, and it is ripe to prepare the technology of tetraalkoxysilane with alkali as a catalyst now, but this method can not obtain to contain the trialkoxy silane of active si-h bond.Containing the trialkoxy silane of activated silica hydrogen bond, only in the presence of copper catalyst, just can make, that its method can be divided into gas-solid phase method is gentle-two kinds of liquid-solid phase methods.The former temperature of reaction height, the trialkoxy silane of generation and alcohol further reaction easily cause trialkoxy silane content to descend, be easy to generate local superheating during reaction, the silica flour sintering reacts many disadvantages such as incomplete, simultaneously the distribution of silicon particle size is had relatively high expectations, it is complicated that engineering is amplified.Gas-liquid-solid phase method is that silica flour is dispersed in the suspension agent of liquid phase, and reacts with gas phase alcohol, and this method makes the Direct Synthesis of Trialkoxysilane reaction realize high transformation efficiency and high selectivity.The research emphasis of this method is mainly aspect two: one, and the selection of suspension agent, two, catalyst system preferred.USP 3,641,077th, are suspension agent with methyl phenyl silicone oil (DC-710), cuprous chloride is a catalyzer, and solid material was reduced two hours in 1050 ℃ hydrogen in advance, makes it sinter Si into: Cu=9: 1 contact, react after grinding, temperature of reaction is 260～280 ℃ again.Its silicon transformation efficiency (η) is 7.6% when reacting with methyl alcohol, and trialkoxy silane content (T) is 55.8% in the alkoxysilane product.When with ethanol synthesis, η=2%, T=80%.The used suspension agent high price of this method, solid phase is handled complicated, and energy consumption is big, and USP 3,77 5, and 457 usefulness polycyclic aromatic hydrocarbonss are made suspension agent, with ethanol synthesis, need to add HF, bring corrosion and murder by poisoning problem.The spy opens clear 74-55,625; 55626; 55,627 synthesis result is also undesirable; The spy opens clear 79-163, and 529 adopt structural formula CXn(Ar)
4-nThe mixture of (X is H or alkyl, n=1,2) is made suspension agent, 220 ℃ of temperature of reaction, product η=93%, T=63%; The spy opens clear 80-76, and 891 is suspension agent with the dodecylbenzene, and 200 ℃ of temperature of reaction obtain η=80%, T=86%; The spy opens clear 82-99, and 593 is suspension agent with the hydrogenation triphen, 240 ℃ of temperature of reaction, and reaction result is η=88.6%, T=87%; The spy opens clear 82-108, and 094 is suspension agent with two undecyl benzene, 240 ℃ of temperature of reaction, and reaction result is η=90%, T=88%; The spy opens clear 82-108, and the different paraffin oil of 095 usefulness is a suspension agent, 240 ℃ of temperature of reaction, reaction result η=86%, T=87%; The spy opens clear 86-1, and 063 makes suspension agent with phenyl ether, 200 ℃ of reactions down, and the result is η=75%, T=90% is if react then η=58%, T=90% under 180 ℃.The spy opens clear 87-286, and 992 is suspension agent with the dodecylbenzene, and cuprous chloride/Red copper oxide (0.495/5.37) is catalyzer, 220 ℃ of reactions down, and the result is η=93%, T=78.4%.By above patent as can be seen, with CXn(Ar)
4-nThough η is higher for suspension agent, T has only 62%, and other patent temperature of reaction is all higher, and some suspension agent price is more expensive, makes suspension agent with phenyl ether, and it is too low that temperature of reaction reduces back η value, and the suspension agent consumption is excessive, and plant factor and spatiotemporal efficiency are all lower.
The objective of the invention is to improve the deficiencies in the prior art, make the synthesis technique of organoalkoxysilane have easy to operation, widen the particle diameter scope of application of raw material silica flour, use suspension agent efficiently cheap and easy to get, temperature of reaction is low, silicon transformation efficiency (η) height, characteristics such as trialkoxy silane yield (T) height and suitable for mass production in the product.
The method for making of trialkoxy silane of the present invention and tetraalkoxysilane is: the solid phase with silica flour and copper catalyst are formed by a certain percentage, add in the vertical reaction tower, and logical rare gas element is warming up to and gives fixed temperature, keeps certain hour to handle.
The a certain amount of solid-phase material input of having handled is filled in the reactor of suspension agent, and dispersed with stirring is adjusted to temperature of reaction, under inert atmosphere, adds Fatty Alcohol(C12-C14 and C12-C18) with certain speed and reacts.Reaction distilled product is analyzed with gas-chromatography, with the terminal point of control reaction.
The silica flour that the present invention is used both can adopt average particle size less than 100 μ m, also can use greater than 150 μ m(100 orders), promptly average particle size is at the silica flour of 20-200 μ m.
The used copper catalyst of the present invention is a metallic copper, cupric oxide, Red copper oxide, copper halide, cuprous halide, Tubercuprose, acetylacetone copper, neutralized verdigris or and composition thereof etc.Catalyst levels is counted the 1-5%(weight of silicon consumption with fine copper), with 2-4%(weight) for well.Also can add an amount of promotor in the catalyzer, to promote reaction, suitable promotor has the compound of metals such as Mn, Co, Sb, Na, and its consumption is the 0-2%(weight of silicon consumption).
The solid phase treatment temp of present method is 200～350 ℃, with 225～300 ℃ for well.Carry out in inert atmosphere during processing, suitable rare gas element has nitrogen, argon or helium etc.Treatment time is advisable with 1.5-2.5 hour usually at 0.5-3 hour.
The used Fatty Alcohol(C12-C14 and C12-C18) of the present invention is the straight or branched alcohols of 1～4 carbon atom such as methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol etc., total consumption of Fatty Alcohol(C12-C14 and C12-C18) is 6-10 times (weight) of silica flour weight, water content in the Fatty Alcohol(C12-C14 and C12-C18) is very big to the influence of reaction, generally need be controlled at below the 1000ppm.
The effect of suspension agent mainly disperseing reaction medium, is distributed reaction heat, prevents to react local superheating etc.Therefore requiring suspension agent is inertia, not with the reactant effect, and Heat stability is good, non-volatile under temperature of reaction, not decompose, thermal conductivity is good, and is nontoxic, and inexpensive, is easy to get, and is easy to reclaim use etc. again.The character of suspension agent is also very big to the good bad influence of dissemination, the suspension agent that the present invention suits has: common used in industry thermal oil such as JD-300, JD-350, YD-132, YD-130(Jiangsu Province Jiangyin chemical industry one factory's product), dodecylbenzene or benzyl toluene class and composition thereof etc.The suspension agent consumption is: suspension agent (volume): silica flour (weight)=1.5～3: 1.Also can add an amount of silicon-containing surfactant in the suspension agent, general consumption is 0.5～5%(volume, based on the suspension agent volume), to improve the spatiotemporal efficiency of plant factor and reaction.
Synthesis reaction temperature generally carries out under 160～250 ℃, with 175～210 ℃ for well.Building-up reactions is to carry out under inert atmosphere (as nitrogen, argon).Fatty Alcohol(C12-C14 and C12-C18) fed time 3-8 hour.
The present invention by suspension agent selection and the improvement of processing condition, operation is simple to make building-up reactions, good reproducibility, suspension agent is inexpensive, be easy to get, consumption is little, equipment spatiotemporal efficiency height.Temperature of reaction is low, generally below 200 ℃, silicon transformation efficiency height, can reach more than 85%, reach as high as 99%, the content of trialkoxy silane is more than 85% in the product, be up to 96%, the distribution of reaction pair silicon particle size requires lower, and subject range is wide, both can adopt average particle size less than 100 μ m, also can use whole warps greater than 150 μ m, promptly average particle size is made raw material at the silica flour of 20～200 μ m, is suitable for engineering to be amplified.
Embodiment one
It is 60mm that solid phase is handled a upper diameter, has outlet, lower diameter is that gas distribution grid is equipped with in 25mm, bottom, and interior dress thermowell carries out in the glass reactor of outer additional heat chuck and automatic temperature control device.With silica flour and copper catalyst [Cu
2O/CuCl=2.86(weight)] press Si: Cu=1: ratio 0.0556(weight), add 42.7 and restrain in reactor, logical nitrogen is warming up to 230 ℃, handles 0.5 hour.
One stirring is housed, filling tube, Fatty Alcohol(C12-C14 and C12-C18) filling tube and condenser, volume are to add dibenzyl toluene-benzyl toluene mixture 140ml in the irony reactor of 300ml, handled solid phase 42.7g, stirring disperses, and conditioned reaction temperature to 200 ℃ fed methyl alcohol 417g in 7 hours, get overhead product 382g, analytical results is T=76%, η=98.8%, space-time yield (J)=645g/KgSih.
Embodiment two
Solid phase prescription and processing, synthesizer, operation are with example 1.YD-132 120ml and above-mentioned solid phase 42.7 gram of having handled are added in the reactors, stir, conditioned reaction temperature to 190 ℃ fed methyl alcohol 325g in 6 hours, and the overhead product analytical results is η=96%, T=92%, J=704g/KgSih.
Embodiment three
Device, operation is with example 1.JD-300 100ml is added in the reactors with 42.7 grams of processing solid phase identical with example 1, stir and decompose, conditioned reaction temperature to 180 ℃, feed methyl alcohol 270g, reacted 5 hours, the analytical results of gained overhead product is η=84%, T=85%, J=748g/KgSih.
Embodiment four
Device, operation, solid phase prescription are handled with example 1.With benzyl toluene class and YD-132 mixed solution [1: the 2(volume ratio)] 140ml with handled solid phase 42.7 grams and be added in the reactor, stirring disperses, conditioned reaction temperature to 200 ℃, feed methyl alcohol 380g, reacted 5.5 hours, gained overhead product analytical results is η=91%, T=68%, J=841g/KgSih.
Embodiment five
Solid phase processing and synthesizer are with example 1.Silica flour and copper catalyst (CuCl) are pressed Si: Cu=1: ratio 0.424(weight) adds in the glass reactor, and logical nitrogen is handled 2h at 260 ℃.
With dibenzyl toluene-benzyl toluene mix suspending agent 100ml with handled solid phase 48g and added in the reactor, dispersed with stirring is heated to 230 ℃ of temperature of reaction, in 4 hours, feed methyl alcohol 320ml, the analytical results of gained overhead product is: η=82%, T=77%, J=796g/KgSih.
Embodiment six
Solid phase processing and synthesizer are with example 1.With CuCl: Cu
2O: MnO
2=8: 1: mixture 1(weight) is a catalyzer, presses Si: Cu=1: ratio 0.15(weight) adds glass reactor, under 230 ℃, handles 0.5 hour.
With dibenzyl toluene-benzyl toluene mixture 120ml, handle solid phase 48g and added reactor, feed ethanol 470g down at 200 ℃, reacted 8 hours, gained overhead product analytical results is: η=86%, T=86%, J=892g/KgSih.
Embodiment seven
Operation, prescription is with example 1.Adopting and reclaiming dibenzyl toluene-benzyl toluene mixed solution 140ml is suspension agent, and reaction result is η=84%, T=84%, J=626g/KgSih.
Embodiment eight
With the 1000g silica flour, under 320 ℃, handled 2 hours in the iron processing unit that 75g CuCl adds.
The above-mentioned solid phase handled added be equipped with in the irony reactor of 3500ml dibenzyl toluene-benzyl toluene mixture, under 240 ℃, feed methyl alcohol 7.5Kg in 4 hours, the analytical results of overhead product is: η=96%, T=50%, J=600g/KgSih.
Claims (10)
1, a kind of by silicon and Fatty Alcohol(C12-C14 and C12-C18) in the presence of copper catalyst, the direct method of synthetic organoalkoxysilane in suspension agent is characterized in that:
(1) by silica flour, the solid phase that 1-5% copper catalyst (heavy based on silica flour, in fine copper) and 0～2% (heavy based on silica flour) promotor are formed is handled 0.5～3h down at 150～420 ℃,
(2) suspension agent (volume): silica flour (weight)=1.5～3: 1,
(3) the Fatty Alcohol(C12-C14 and C12-C18) consumption is heavy 6～8 times of silica flour,
(4) temperature of reaction is 160～250 ℃,
(5) 3～8 hours reaction times,
2, according to the described method of claim 1, it is characterized in that used copper catalyst is metallic copper, Red copper oxide, copper halide, cuprous halide or and composition thereof.
3,, it is characterized in that used promotor is Mn, Co, Sb, or the compound of Na according to the described method of claim 1.
4, according to claim 1 or 2 described methods, it is characterized in that the copper catalyst consumption be 2 heavy～4%(of silica flour in fine copper, weight).
5,, it is characterized in that the solid phase treatment temp is 225～300 ℃ according to the described method of claim 1.
6,, it is characterized in that the solid phase treatment time is 1.5～2.5b according to the described method of claim 1.
7, according to the described method of claim 1, it is characterized in that used suspension agent is industrial thermal oil JD-300, JD-350, YD-132, YD-130, dodecylbenzene, or the benzyl toluene class and composition thereof.
8, according to claim 1 or 7 described methods, it is characterized in that being added with in the suspension agent 0.5～5%(volume, based on the suspension agent volume) silicon-containing surfactant.
9,, it is characterized in that used Fatty Alcohol(C12-C14 and C12-C18) is the straight or branched Fatty Alcohol(C12-C14 and C12-C18) of 1～4 carbon atom according to the described method of claim 1.
10,, it is characterized in that temperature of reaction is 175～210 ℃ according to the described method of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 92108098 CN1027508C (en) | 1992-04-23 | 1992-04-23 | Direct method for synlhesis of alkoxy silane |
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| CN 92108098 CN1027508C (en) | 1992-04-23 | 1992-04-23 | Direct method for synlhesis of alkoxy silane |
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| CN1027508C CN1027508C (en) | 1995-01-25 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368416C (en) * | 2006-02-22 | 2008-02-13 | 江阴市金山化工有限公司 | Production process of triethoxy silane |
| CN101885858A (en) * | 2009-05-12 | 2010-11-17 | 自贡市川友新材料有限公司 | Plastic filling agent and preparation method thereof |
| CN101096374B (en) * | 2006-06-30 | 2012-08-15 | 张家港市国泰华荣化工新材料有限公司 | Method for synthesizing alkoxy silane directly by silanol |
| CN102762579A (en) * | 2010-02-22 | 2012-10-31 | 瓦克化学股份公司 | Method for producing ester-functional silanes |
| CN103797018A (en) * | 2011-09-06 | 2014-05-14 | Oci有限公司 | Method for preparing trialkoxysilane |
| CN104387413A (en) * | 2014-11-03 | 2015-03-04 | 湖北武大有机硅新材料股份有限公司 | Production method for preparing trialkoxysilane by adopting direct method |
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| CN110862407A (en) * | 2019-11-27 | 2020-03-06 | 鑫创新材料科技(徐州)有限公司 | Preparation method of alkoxy silane |
| CN113416207A (en) * | 2021-07-05 | 2021-09-21 | 华陆工程科技有限责任公司 | Method for producing alkyl orthosilicate from silicon powder by one-step method |
| CN115672363A (en) * | 2022-09-27 | 2023-02-03 | 中触媒新材料股份有限公司 | Catalyst for synthesizing tetramethoxysilane and preparation method and application thereof |
-
1992
- 1992-04-23 CN CN 92108098 patent/CN1027508C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368416C (en) * | 2006-02-22 | 2008-02-13 | 江阴市金山化工有限公司 | Production process of triethoxy silane |
| CN101096374B (en) * | 2006-06-30 | 2012-08-15 | 张家港市国泰华荣化工新材料有限公司 | Method for synthesizing alkoxy silane directly by silanol |
| CN101885858A (en) * | 2009-05-12 | 2010-11-17 | 自贡市川友新材料有限公司 | Plastic filling agent and preparation method thereof |
| CN101885858B (en) * | 2009-05-12 | 2013-05-22 | 自贡市川友新材料有限公司 | Plastic filling agent and preparation method thereof |
| CN102762579A (en) * | 2010-02-22 | 2012-10-31 | 瓦克化学股份公司 | Method for producing ester-functional silanes |
| CN103797018A (en) * | 2011-09-06 | 2014-05-14 | Oci有限公司 | Method for preparing trialkoxysilane |
| CN104387413A (en) * | 2014-11-03 | 2015-03-04 | 湖北武大有机硅新材料股份有限公司 | Production method for preparing trialkoxysilane by adopting direct method |
| CN104387413B (en) * | 2014-11-03 | 2017-03-15 | 湖北武大有机硅新材料股份有限公司 | A kind of direct method prepares the production method of trialkoxy silane |
| CN110745834A (en) * | 2019-11-27 | 2020-02-04 | 鑫创新材料科技(徐州)有限公司 | Green production process and application of aerogel |
| CN110862407A (en) * | 2019-11-27 | 2020-03-06 | 鑫创新材料科技(徐州)有限公司 | Preparation method of alkoxy silane |
| CN110745834B (en) * | 2019-11-27 | 2021-09-10 | 鑫创新材料科技(徐州)有限公司 | Green production process and application of aerogel |
| CN113416207A (en) * | 2021-07-05 | 2021-09-21 | 华陆工程科技有限责任公司 | Method for producing alkyl orthosilicate from silicon powder by one-step method |
| CN115672363A (en) * | 2022-09-27 | 2023-02-03 | 中触媒新材料股份有限公司 | Catalyst for synthesizing tetramethoxysilane and preparation method and application thereof |
| CN115672363B (en) * | 2022-09-27 | 2024-05-14 | 中触媒新材料股份有限公司 | Catalyst for synthesizing tetramethoxysilane and preparation method and application thereof |
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| CN1027508C (en) | 1995-01-25 |
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