CN104151347A - Method for preparing dimethyl cyclosiloxane from dimethyl ether/silicon powder by one-step process - Google Patents
Method for preparing dimethyl cyclosiloxane from dimethyl ether/silicon powder by one-step process Download PDFInfo
- Publication number
- CN104151347A CN104151347A CN201410249961.6A CN201410249961A CN104151347A CN 104151347 A CN104151347 A CN 104151347A CN 201410249961 A CN201410249961 A CN 201410249961A CN 104151347 A CN104151347 A CN 104151347A
- Authority
- CN
- China
- Prior art keywords
- silica flour
- dme
- dimethyl cyclosiloxane
- treatment
- dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention relates to a method for preparing dimethyl cyclosiloxane from dimethyl ether/silicon powder by a one-step process. The method comprises the following steps of firstly carrying out pretreatment and activation treatment on silicon powder, adding the treated silicon powder and a solvent into a reactor together, mixing well, closing, heating to a predetermined temperature, introducing a certain amount of methyl bromide, and then metrically introducing dimethyl ether into a reactor and carrying out one-step reaction on dimethyl ether/silicon powder to obtain dimethyl cyclosiloxane, when key indexes such as the selection rate of DMC and the conversion rates of silicon powder and dimethyl ether are respectively 80%, 90% and 90%, stopping reaction, and recovering the solvent to prepare the dimethyl cyclosiloxane finished product. In the entire process, the key indexes such as the selection rate of DMC and the composition of the unreacted mixed gas are subjected to online monitoring by virtue of gas chromatography.
Description
Technical field
The present invention relates to the production technical field of silicone intermediate, be specifically related to a kind of method that dme/silica flour single stage method is prepared dimethyl cyclosiloxane.
Background technology
The kind of current high performance new chemical materials-organosilicon material has exceeded 10000 kinds, can with product just have more than 5000 kinds, mainly comprise high temperature silicon rubber, room temperature silicon rubber, silicone oil and secondary processing product, silicone resin and silane coupling agent etc.High temperature silicon rubber is widely used in aviation and aerospace industry, automotive industry, electronic apparatus; Room temperature silicon rubber is for building industry, electronic industry, road construction, as materials such as sealing, bonding perfusion, coatings; Silicone resin is because of its splendid thermotolerance, and good electrical insulating property, chemical-resistant resistance and hydrophobic nature, flame retardant resistance, mainly as heat resistant varnish, high-temperature resistant coating, tackiness agent, weather-resistant coating and hydrophobic coating.Organosilicon material development in recent years rapidly, except Asian market keeps the annual growth of 12%-15%, the organosilicon market that the U.S. and West Europe etc. are the most ripe, its tempo, also higher than the growth of its GDP, reaches 4%～6%, global amplification maximum be China, exceed 25%, within 2009, Chinese organosilicon material consumption just exceedes 400,000 tons, and exceeding the U.S. becomes the maximum country of consumption of organosilicon material, accounts for 30% of global consumption.At present the organosilicon material output in the whole world exceedes 1,350,000 tons, most developed countries all using organosilicon material as 21 century novel material emphasis developed.
Estimate that in a few years from now on, the average growth rate per annum of global organosilicon demand is about 6%, the average growth rate per annum of China's organosilicon consumption will keep 20% left and right.Along with the fast development of the industry such as the electric industry of recent year, building and automotive industry, textile printing and dyeing, silicone industry in China product consumption sharply increases, the industry pillar of organosilicon industry is the production of the polysiloxane of basis, upstream intermediate raw material-Primary Speciation, and domestic production capacity deficiency causes all needing every year the silicone monomers product of a large amount of import Primary Speciations.In these products, more than 90% be dimethyl cyclosiloxane (being called for short DMC), DMC really can be directly used in the synthetic main raw material of downstream fine product in organosilicon industry, be also the source of profit that organosilane monomer corporate boss wants simultaneously.It is predicted, after 2014, domestic monomer export volume can increase gradually, and the DMC of high added value and portion downstream product thereof will have wide market outlook.Therefore, DMC synthetic technology level height directly affects the ups and downs of organosilicon industry, and countries in the world all give special concern.
The forties in last century, Rochow has invented the direct technology of preparing of Halogen of DMC, and this technology has that raw material is easy to get, solvent-free, space-time yield is high, easily realize the advantages such as serialization production, once appearance, develops rapidly and becomes the main flow of DMC production technology.
The direct preparation technology of DMC Halogen is: taking Pure Silicon Metal and methyl chloride as raw material, copper is catalyzer, and direct reaction generates methyl chlorosilane mix monomer.Synthetic mix monomer, through high precision rectification, is isolated a series of methyl chlorosilane monomers, and wherein dimethyldichlorosilane(DMCS) accounts for the 80-93% of total amount.The further hydrolysis of this product, cracking, rectifying can be prepared DMC.And the by product HCl of the methyl chlorosilane monomer hydrolysis recovery of purifying, making methyl chloride synthesizes for monomer again, has formed the cycle applications of chlorine element in each workshop section in whole technical process.Above-mentioned technological process as shown in Figure 1.
Although the direct technology of preparing advantages of above-mentioned DMC Halogen, industrial application is extensive.But also there is long flow path, complex process equipment, the drawbacks such as production control difficulty.Simultaneously the recycling of chlorine element (cyclic utilization rate is 70%-80% only) in production process, not only increases expense, and causes a large amount of HCl to produce, etching apparatus, contaminate environment.Therefore in this sustained economic development, energy growing tension, day by day serious epoch of pollution, the green synthetic replacement technology of development DMC is extremely urgent.
Current research is found, adopts metallic silicon power and dme, taking copper as catalyzer, under non-halogen condition, can prepare DMC by single step reaction.The intrinsic drawback that this technique has not only avoided chlorine element to recycle in above-mentioned traditional technology, and process and equipment simple, control easily, therefore there is significant technical advance and prospects for commercial application, and will start new era of DMC green synthesis techniques.DMC Halogen direct method technological invention people Rochow also once foretold: " non-halogenated direct method is prepared with organic siloxane, will be the most challenging work in future ".
Summary of the invention
Problem to be solved by this invention is to provide a kind of dme/silica flour single stage method to prepare the method for dimethyl cyclosiloxane, the method is under monobromethane and high boiling solvent existence, adopting dme and silica flour is reactant, CuCl/ZnO/Sn is catalyzer, carry out slurry polymerization, single stage method is prepared DMC, and this reaction equation is shown below:
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: a kind of dme/silica flour single stage method is prepared the method for dimethyl cyclosiloxane, it is characterized in that, comprises the steps:
(1) the pre-treatment of raw material: the dry pre-treatment of dme and monobromethane, in the exit passageway of dme and monobromethane storage tank, add a segment molecule screen casing before entering reactor, remove contained minor amount of water in dme and monobromethane raw material; The pre-treatment of silica flour, takes hydrofluoric acid solution and silica flour that weight ratio is 4～6:1, at room temperature stirs 0.5～1.5 hour, filters, and fully washs with dehydrated alcohol, and vacuum-drying 2～8 hours at 60～90 DEG C, removes the SiO of silicon powder surface layer
2, for subsequent use;
(2) the activation treatment of silica flour: the silica flour in catalyst mixture and step (1) is fully mixed according to weight ratio 1～5:100, and mixture is processed 1～5 minute through 80～140 DEG C of vacuum sinterings 1～6 hour or with microwave oven, obtains activating silica flour;
(3) dimethyl cyclosiloxane synthetic and separating: after the activation silica flour in solvent and step (2) is fully mixed according to weight ratio 1～5:1, add together in reactor, mix, airtight, pressure is 0.1～0.3MPa, be warming up to 260 DEG C～300 DEG C, pass into the monobromethane in step (1), the weight ratio of the activation silica flour in monobromethane and step (2) is 0.05～0.15:1, then in reactor, pass into metering dme, the intake velocity of dme is 50～80 Grams Per Hours, stirring velocity is 200～1000 revs/min, the mixture that reaction generates is separated and is obtained high boiler material and lower boiling material by separator column, high boiler material passes back into reactor, lower boiling material needs further condensation, wherein the methylsiloxane mixture phlegma in lower boiling material enters after rectifier unit separates and obtains dimethyl cyclosiloxane, in lower boiling material the complete dme of unreacted and the monobromethane that do not consume further compression collect, after successive reaction 10～30 hours, the selection rate of dimethyl cyclosiloxane reaches 80～90%, and the transformation efficiency of silica flour reaches 90～95%, the transformation efficiency of dme reaches 90～95%, stopped reaction, reclaims solvent, finally prepares dimethyl cyclosiloxane product.
Because CH3Br circulates and recycles in reaction process, therefore above formula also can represent with formula I:
Preferably, the silica flour in the pre-treatment step of described raw material is the silica flour of size 50～500 μ m.
Preferably, the catalyst mixture in described activation treatment step is made up of catalyzer and promotor, and catalyzer is preferably neutralized verdigris, copper hydroxide, in cuprous chloride a kind of or more than one; Promotor is preferably a kind of in zinc oxide and tin or its combination, and the part by weight of catalyzer and promotor is 50:1～3.
Preferably, described activation treatment is cryogenic vacuum pre-treatment or Microwave Pretreatment, cryogenic vacuum pre-treatment is to add in crucible after silica flour and catalyzer are fully ground according to weight ratio 1～5:100, be placed in vacuum drying oven, vacuumize, rising temperature to 80～140 DEG C, are incubated 1～6 hour; Microwave Pretreatment is to add in crucible after silica flour and catalyst mixture are fully ground according to weight ratio 1～5:100, is inserted in microwave oven, and the power of microwave oven is 800-1500W, and the time of microwave treatment is 1～5 minute.
Preferably, the solvent in the synthesis step of described dimethyl cyclosiloxane is paraffin oil, dodecylbenzene, two (undecyl) benzene etc. a kind of or more than one.
Preferably, the weight ratio of the solvent/silica flour in the synthesis step of described dimethyl cyclosiloxane is preferably 1～5:1.
Preferably, the temperature in the synthesis step of described dimethyl cyclosiloxane is preferably 270 DEG C～290 DEG C.
After reacting completely, carry out the quantitative analysis of selectivity of product by vapor-phase chromatography, calculate the selectivity of DMC; Filtering reacting liquid body obtains solid residue, and washing is dry, the remaining solid masses of weighing, the transformation efficiency of calculating silica flour and dme, the yield of DMC product.With the transformation efficiency of silica flour and dme, the selectivity of DMC and yield are evaluated the quality of synthetic technological condition.
1. the amount (mmol) × 100% of silica flour in the amount (mmol) of silica flour/input reactor in the transformation efficiency of silica flour=siliceous reaction product.
2. the amount (mmol) × 100% of dme in the amount (mmol) of dme/input reactor in the transformation efficiency of dme=siliceous reaction product.
3. the amount (mmol) × 100% of amount (the mmol)/siliceous reaction product of selectivity=generation cyclosiloxane of DMC.
4. the amount (mmol) × 100% of silica flour in the amount (mmol) of yield=generation cyclosiloxane of DMC/input reactor.
Dme/silica flour single stage method of the present invention is prepared the method for dimethyl cyclosiloxane, the method is first silica flour to be carried out after pre-treatment and activation treatment, add together with solvent in reactor, airtight, heat up, be raised to after specified temperature, pass into a certain amount of monobromethane, then in reactor, pass into dme continuous measurement, carry out non-halogenated method one-step synthesis reaction, the mixture that reaction generates is separated into high boiler material and lower boiling material by separator column again, high boiler material again circulates and enters reactor after refluxing, lower boiling material needs further condensation, wherein the methylsiloxane phlegma in lower boiling material enters rectifier unit and isolates dimethyl cyclosiloxane, in lower boiling material, the complete dme of unreacted and the monobromethane that do not consume further compress collection.After successive reaction certain hour, when the key indexs such as the transformation efficiency of the selection rate of DMC, silica flour and dme reach respectively more than 80%, 90% and 90%, stopped reaction, reclaims solvent, finally prepares dimethyl cyclosiloxane product.The key index such as selection rate, the composition of unreacted mixed gas of vapor-phase chromatography on-line monitoring DMC for whole process.
Brief description of the drawings
Fig. 1 be prior art dimethyl cyclosiloxane the direct preparation method of Halogen.
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for the present invention is described.The implementation condition adopting in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
Describe the present invention in detail below in conjunction with embodiment, should be appreciated that described herein giving an example only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
The pre-treatment of raw material: the dry pre-treatment of dme and monobromethane, in the exit passageway of dme and monobromethane storage tank, add a segment molecule screen casing before entering reactor, remove contained minor amount of water in dme and monobromethane raw material; The pre-treatment of silica flour, takes hydrofluoric acid solution that weight ratio is 5:1 and the silica flour of 250 μ m, at room temperature stirs 1 hour, filters, and fully washs with dehydrated alcohol, and vacuum-drying 5 hours at 80 DEG C, removes the SiO of silicon powder surface layer
2, for subsequent use;
The activation treatment of silica flour: after CuCl, ZnO and Sn are mixed according to weight ratio 50:1:1, obtain catalyst mixture, this catalyst mixture and above-mentioned silica flour are fully mixed according to weight ratio 2:100, mixture is processed 3 minutes with microwave oven, obtains activating silica flour again;
Dimethyl cyclosiloxane synthetic and separating: after dodecylbenzene and above-mentioned activation silica flour are fully mixed according to weight ratio 2:1, add together in reactor, airtight, the pressure in reactor is 0.2MPa, is warming up to 280 DEG C, pass into monobromethane, the weight ratio that ensures monobromethane and above-mentioned activation silica flour is 0.1:1, then in reactor, passes into dme continuous measurement, and the intake velocity of dme is 65 Grams Per Hours, stirring velocity is 800 revs/min, carries out continuous reaction; The mixture that reaction generates is separated and is obtained high boiler material and lower boiling material by separator column, high boiler material passes back into reactor, lower boiling material needs further condensation, wherein the methylsiloxane mixture phlegma in lower boiling material enters after rectifier unit separates and obtains dimethyl cyclosiloxane, in lower boiling material the complete dme of unreacted and the monobromethane that do not consume further compression collect, be again cycled to used in successive reaction; After successive reaction 20 hours, the instant selection rate of dimethyl cyclosiloxane, after the transformation efficiency of silica flour and dme acquires a certain degree, stopped reaction, reclaims solvent, finally prepares dimethyl cyclosiloxane product.
After reaction finishes, the selection rate of on-line determination reaction product DMC, and silica flour and dimethyl ether conversion rate, the results are as follows:
Embodiment 2:
The pre-treatment of raw material: the dry pre-treatment of dme and monobromethane, in the exit passageway of dme and monobromethane storage tank, add a segment molecule screen casing before entering reactor, remove contained minor amount of water in dme and monobromethane raw material; The pre-treatment of silica flour, takes hydrofluoric acid solution that weight ratio is 5:1 and the silica flour of 250 μ m, at room temperature stirs 1 hour, filters, and fully washs with dehydrated alcohol, and vacuum-drying 5 hours at 80 DEG C, removes the SiO of silicon powder surface layer
2, for subsequent use;
The activation treatment of silica flour: after CuCl, ZnO and Sn are mixed according to weight ratio 50:1:1, obtain catalyst mixture, this catalyst mixture and above-mentioned silica flour are fully mixed according to weight ratio 2:100, mixture is processed 3 minutes with microwave oven, obtains activating silica flour again;
Dimethyl cyclosiloxane synthetic and separating: after dodecylbenzene and above-mentioned activation silica flour are fully mixed according to weight ratio 2:1, add together in reactor, airtight, the pressure in reactor is 0.2MPa, is warming up to 290 DEG C, pass into monobromethane, the weight ratio that ensures monobromethane and above-mentioned activation silica flour is 0.1:1, then in reactor, passes into dme continuous measurement, and the intake velocity of dme is 65 Grams Per Hours, stirring velocity is 1000 revs/min, carries out continuous reaction; The mixture that reaction generates is separated and is obtained high boiler material and lower boiling material by separator column, high boiler material passes back into reactor, lower boiling material needs further condensation, wherein the methylsiloxane mixture phlegma in lower boiling material enters after rectifier unit separates and obtains dimethyl cyclosiloxane, in lower boiling material the complete dme of unreacted and the monobromethane that do not consume further compression collect, be again cycled to used in successive reaction; After successive reaction 18 hours, the instant selection rate of dimethyl cyclosiloxane, after the transformation efficiency of silica flour and dme acquires a certain degree, stopped reaction, reclaims solvent, finally prepares dimethyl cyclosiloxane product.
After reaction finishes, the selection rate of on-line determination reaction product DMC, and silica flour and dimethyl ether conversion rate, the results are as follows:
Embodiment 3:
The pre-treatment of raw material: the dry pre-treatment of dme and monobromethane, in the exit passageway of dme and monobromethane storage tank, add a segment molecule screen casing before entering reactor, remove contained minor amount of water in dme and monobromethane raw material; The pre-treatment of silica flour, takes hydrofluoric acid solution that weight ratio is 5:1 and the silica flour of 250 μ m, at room temperature stirs 1 hour, filters, and fully washs with dehydrated alcohol, and vacuum-drying 5 hours at 80 DEG C, removes the SiO of silicon powder surface layer
2, for subsequent use;
The activation treatment of silica flour: after CuCl and ZnO are mixed according to weight ratio 50:1, obtain catalyst mixture, then this catalyst mixture and above-mentioned silica flour are fully mixed according to weight ratio 2:100, microwave oven is processed 3 minutes for mixture, obtains activating silica flour;
Dimethyl cyclosiloxane synthetic and separating: will pair (undecyl) benzene and after above-mentioned activation silica flour fully mixes according to weight ratio 2:1, add together in reactor, airtight, pressure in reactor is 0.2MPa, be warming up to 280 DEG C, pass into monobromethane, the weight ratio that ensures monobromethane and above-mentioned activation silica flour is 0.1:1, then in reactor, pass into dme continuous measurement, the intake velocity of dme is 65 Grams Per Hours, stirring velocity is 800 revs/min, carries out continuous reaction; The mixture that reaction generates is separated and is obtained high boiler material and lower boiling material by separator column, high boiler material passes back into reactor, lower boiling material needs further condensation, wherein the methylsiloxane mixture phlegma in lower boiling material enters after rectifier unit separates and obtains dimethyl cyclosiloxane, in lower boiling material the complete dme of unreacted and the monobromethane that do not consume further compression collect, be again cycled to used in successive reaction; After successive reaction 20 hours, the instant selection rate of dimethyl cyclosiloxane, after the transformation efficiency of silica flour and dme acquires a certain degree, stopped reaction, reclaims solvent, finally prepares dimethyl cyclosiloxane product.
After reaction finishes, the selection rate of on-line determination reaction product DMC, and silica flour and dimethyl ether conversion rate, the results are as follows:
Above-mentioned example is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations that spirit is done according to the present invention or modification, within all should being encompassed in protection scope of the present invention.
Claims (7)
1. dme/silica flour single stage method is prepared the method for dimethyl cyclosiloxane, it is characterized in that, comprises the steps:
(1) the pre-treatment of raw material: the dry pre-treatment of dme and monobromethane, before entering reactor, dme and monobromethane add a segment molecule screen casing, remove contained minor amount of water in dme and monobromethane raw material; The pre-treatment of silica flour, takes hydrofluoric acid solution and silica flour that weight ratio is 4～6:1, at room temperature stirs 0.5～1.5 hour, filters, and fully washs with dehydrated alcohol, and vacuum-drying 2～8 hours at 60～90 DEG C, removes the SiO of silicon powder surface layer
2, for subsequent use;
(2) the activation treatment of silica flour: the silica flour in catalyst mixture and step (1) is fully mixed according to weight ratio 1～5:100, and cryogenic vacuum pre-treatment or Microwave Pretreatment, obtain activating silica flour;
(3) dimethyl cyclosiloxane synthetic and separating: after the activation silica flour in solvent and step (2) is fully mixed according to weight ratio 1～5:1, add together in reactor, mix, airtight, pressure is 0.1～0.3MPa, be warming up to 260 DEG C～300 DEG C, pass into the monobromethane in step (1), the weight ratio of the activation silica flour in monobromethane and step (2) is 0.05～0.15:1, then in reactor, pass into metering dme, the intake velocity of dme is 50～80 Grams Per Hours, stirring velocity is 200～1000 revs/min, the mixture that reaction generates is separated and is obtained high boiler material and lower boiling material by separator column, high boiler material passes back into reactor, lower boiling material needs further condensation, wherein the methylsiloxane mixture phlegma in lower boiling material enters after rectifier unit separates and obtains dimethyl cyclosiloxane, in lower boiling material the complete dme of unreacted and the monobromethane that do not consume further compression collect, after successive reaction 10～30 hours, the selection rate of dimethyl cyclosiloxane reaches 80～90%, and the transformation efficiency of silica flour reaches 90～95%, the transformation efficiency of dme reaches 90～95%, and stopped reaction reclaims solvent, finally prepare dimethyl cyclosiloxane product
Its reaction formula is formula I
2. dme/silica flour single stage method according to claim 1 is prepared the method for dimethyl cyclosiloxane, it is characterized in that, the silica flour in the pre-treatment of described step (1) raw material is the silica flour of size 50～500 μ m.
3. dme/silica flour single stage method according to claim 1 is prepared the method for dimethyl cyclosiloxane, it is characterized in that, catalyst mixture in described step (2) activation treatment step is made up of catalyzer and promotor, catalyzer is neutralized verdigris, copper hydroxide, in cuprous chloride a kind of or more than one; Promotor is zinc oxide or tin or its combination, and the part by weight of catalyzer and promotor is 50:1～3.
4. dme/silica flour single stage method according to claim 1 is prepared the method for dimethyl cyclosiloxane, it is characterized in that, described step (2) activation treatment is cryogenic vacuum pre-treatment or Microwave Pretreatment, cryogenic vacuum pre-treatment is to add in crucible after silica flour and catalyzer are fully ground according to weight ratio 1～5:100, be placed in vacuum drying oven, vacuumize, rising temperature to 80～140 DEG C, are incubated 1～6 hour; Microwave Pretreatment is to add in crucible after silica flour and catalyst mixture are fully ground according to weight ratio 1～5:100, is inserted in microwave oven, and the power of microwave oven is 800-1500W, and the time of microwave treatment is 1～5 minute.
5. dme/silica flour single stage method according to claim 1 is prepared the method for dimethyl cyclosiloxane, it is characterized in that, solvent in the synthesis step (3) of described dimethyl cyclosiloxane is paraffin oil, dodecylbenzene, two undecyl benzene etc. a kind of or more than one.
6. dme/silica flour single stage method according to claim 1 is prepared the method for dimethyl cyclosiloxane, it is characterized in that, the weight ratio of the solvent/silica flour in the synthesis step (3) of described dimethyl cyclosiloxane is 1～5:1.
7. dme/silica flour single stage method according to claim 1 is prepared the method for dimethyl cyclosiloxane, it is characterized in that, the temperature in the synthesis step (3) of described dimethyl cyclosiloxane is 270 DEG C～290 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410249961.6A CN104151347A (en) | 2014-06-06 | 2014-06-06 | Method for preparing dimethyl cyclosiloxane from dimethyl ether/silicon powder by one-step process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410249961.6A CN104151347A (en) | 2014-06-06 | 2014-06-06 | Method for preparing dimethyl cyclosiloxane from dimethyl ether/silicon powder by one-step process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104151347A true CN104151347A (en) | 2014-11-19 |
Family
ID=51877000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410249961.6A Pending CN104151347A (en) | 2014-06-06 | 2014-06-06 | Method for preparing dimethyl cyclosiloxane from dimethyl ether/silicon powder by one-step process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104151347A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088669A (en) * | 1977-04-08 | 1978-05-09 | Dow Corning Corporation | Method for preparing organosilicon compounds from elemental silicon and hydrocarbon ethers |
| US4593114A (en) * | 1984-09-13 | 1986-06-03 | Union Carbide Corporation | Direct process for preparing dimethylsiloxanes |
| US20070249855A1 (en) * | 2006-04-22 | 2007-10-25 | Bernard Kanner And George A. Skoler, Partnership | Novel direct process |
| CN101353356A (en) * | 2008-09-22 | 2009-01-28 | 哈尔滨工业大学 | Method for directly synthesizing trialkoxysilane |
| CN103558315A (en) * | 2013-10-14 | 2014-02-05 | 中山大学 | Preparation technology of dimethylcyclosiloxane mixed standard substance and application of dimethylcyclosiloxane mixed standard substance used as a qualitative standard substance |
-
2014
- 2014-06-06 CN CN201410249961.6A patent/CN104151347A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088669A (en) * | 1977-04-08 | 1978-05-09 | Dow Corning Corporation | Method for preparing organosilicon compounds from elemental silicon and hydrocarbon ethers |
| US4593114A (en) * | 1984-09-13 | 1986-06-03 | Union Carbide Corporation | Direct process for preparing dimethylsiloxanes |
| US20070249855A1 (en) * | 2006-04-22 | 2007-10-25 | Bernard Kanner And George A. Skoler, Partnership | Novel direct process |
| CN101353356A (en) * | 2008-09-22 | 2009-01-28 | 哈尔滨工业大学 | Method for directly synthesizing trialkoxysilane |
| CN103558315A (en) * | 2013-10-14 | 2014-02-05 | 中山大学 | Preparation technology of dimethylcyclosiloxane mixed standard substance and application of dimethylcyclosiloxane mixed standard substance used as a qualitative standard substance |
Non-Patent Citations (1)
| Title |
|---|
| 周安安等: "非卤直接法制备硅氧烷材料的研究进展", 《浙江科技学院学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102372733B (en) | Continuous preparation method for methyl trialkoxysilane | |
| CN101824046B (en) | Method for generating dimethyldichlorosilance by utilizing disproportionation reaction | |
| CN103288865B (en) | A kind of method utilizing organic silicon azeotrope to produce tetraethoxy | |
| CN103145992B (en) | Vinyl silicon material as well as preparation method and application of vinyl silicon material in preparation of solventless insulating paint of high-temperature motor | |
| CN110745834B (en) | Green production process and application of aerogel | |
| CN105131028A (en) | Preparation method of methyl triethoxysilane | |
| CN104926853A (en) | Preparation method of propylene acyloxy propyl trialkoxy silane | |
| CN102924504A (en) | Preparation method of propyl trimethoxy silane | |
| CN107226909A (en) | A kind of fabric softener epoxy modified polysiloxane preparation method processed | |
| CN102863465A (en) | Preparation method for methyl phenyl di-alkoxy silane | |
| CN103319519B (en) | A kind of method utilizing organic silicon azeotrope production hexamethyldisiloxane | |
| CN104151346A (en) | Method for producing dimethyl cyclosiloxane in non-halogenation direct continuous mode | |
| CN104558611A (en) | MDTQ silicon resin, as well as preparation method and application thereof | |
| CN102250133B (en) | Method for preparing dimethyl dichlorosilane by using disproportionation method | |
| CN103788124B (en) | A kind of method of purification of electron level octamethylcy-clotetrasiloxane | |
| CN103333200B (en) | A kind of synthetic method of normal-butyl aminopropyltrialkoxysilane | |
| CN104151347A (en) | Method for preparing dimethyl cyclosiloxane from dimethyl ether/silicon powder by one-step process | |
| CN102757458A (en) | Method and device for preparing tetramethyldihydrodisiloxane | |
| CN104371108B (en) | A kind of non-halogen non-phosphate Silicone-containing Flame Retardant and preparation method thereof | |
| CN105254658A (en) | Preparation method for methyl trialkoxy silane | |
| CN107090220A (en) | A kind of solar energy heat absorbing coating and preparation method thereof | |
| CN106008587A (en) | Method for producing dimethyl cyclosiloxane from silicone rubber scraps | |
| CN106699800A (en) | Preparation method of methyl trialkoxysilane | |
| CN104925815A (en) | Device and method for treating silane exhaust through reactive distillation | |
| CN105085921A (en) | Method for preparing methyl hydrogen silicone oil from organic silicon by-product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141119 |