CN1594400A - Process for preparing high boiling silicone oil by using organic high boiling point matter - Google Patents
Process for preparing high boiling silicone oil by using organic high boiling point matter Download PDFInfo
- Publication number
- CN1594400A CN1594400A CN 200410013358 CN200410013358A CN1594400A CN 1594400 A CN1594400 A CN 1594400A CN 200410013358 CN200410013358 CN 200410013358 CN 200410013358 A CN200410013358 A CN 200410013358A CN 1594400 A CN1594400 A CN 1594400A
- Authority
- CN
- China
- Prior art keywords
- boiling
- parts
- high boiling
- reaction
- fluxing agent
- 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.)
- Granted
Links
Images
Abstract
The invention discloses a process for preparing high boiling silicone oil by using organic high boiling point matter which consists of, dropping methanol into organosilicon high boiling substance for alcoholysis reaction at normal temperature, the hydrogen chloride produced in the dropping reaction procedure entering exhausting apparatus and being transferred into water drenching tower for absorption, then charging in urea, flux and ammonium bicarbonate into neutralizing system to dissolve the hydrogen chloride, stewing for stratification, separating the lower layer liquid congruent melting substance and the top layer crude product, filtering, thus obtaining silicone oil product with high boiling point.
Description
Technical Field
The invention relates to a production method for producing methoxysilane by using chlorosilane, in particular to a production method for producing high-boiling silicone oil by using organosilicon high-boiling components.
Background
With the rapid development of the world organic silicon industry, the demand for methyl chlorosilane is more and more, silane high-boiling-point substances, which are byproducts generated in the synthesis process of methyl chlorosilane monomers, are more and more, the commercial value of the high-boiling-point substances is low all the time, and a large amount of high-boiling-point substances are accumulated to block a warehouse, so that not only are serious environmental protection problems and safety problems caused, but also a large amount of effective resources are wasted. Therefore, the use of high boiling substances has become a serious obstacle to the further development of the organosilicon industry.
At present, a plurality of units at home and abroad do a great deal of work on the comprehensive utilization of high-boiling residues, and the adopted methods mainly comprise a cracking method, a hydrolysis method and an alcoholysis method, but the methods have the problems of difficult reaction control, complex process, unstable product performance and the like at different degrees: if the cracking method is used for preparing monosilane, the reaction conditions are harsh, the content of dimethyldichlorosilane in the product is low, and high-boiling residues need to be distilled firstly, otherwise, solid residues in the products are easy to cause catalyst poisoning; the hydrolysis method has the defects of difficult washing of products, unstable quality and the like; the existing alcoholysis method has the problems of difficult control of molecular weight, difficult separation oftarget products and the like.
The invention aims to provide a preparation method for synthesizing high-boiling silicone oil by using organic silicon high-boiling residues, which has the advantages of short flow, easy industrial production, controllable molecular weight and stable quality.
The technical scheme of the invention is as follows:
the raw material ratio is as follows: (parts by weight)
50-60 parts of organic silicon high-boiling-point substance 100 methanol and 60-70 parts of urea
30-40 parts of 6-13 parts of ammonium bicarbonate serving as fluxing agent
The fluxing agent is zinc oxide, zinc chloride and zinc carbonate.
When the fluxing agent is zinc oxide, the raw material proportion is 6-8 parts by weight.
When the fluxing agent is zinc carbonate, the raw material proportion is 9-12 parts by weight
When the fluxing agent is zinc chloride, the raw material proportion is 10-13 parts by weight.
The organosilicon high-boiling substance is commonly called high-boiling substance and high-boiling monomer, and is used for directly synthesizing methyl chlorideThe silane byproduct has a boiling range of 80-215 ℃ and a main chain of-Si-Si-, Si-O-Si-or/and Si-CH2-Si-, etc. chlorosilane mixtures.
Secondly, the preparation process comprises the following steps:
① alcoholysis step, dripping methanol into the organosilicon high-boiling residue, and carrying out alcoholysis reaction at normal temperature, wherein the reaction process is as follows:
main reaction:
side reaction:
side reaction:
the methanol dripping time is 1-2 hours, hydrogen chloride gas generated in the dripping reaction process is sent into an acid recovery device through an air draft device to be absorbed, and deacidification is continued for 2-3 hours after dripping is finished;
② neutralization step, adding urea, fluxing agent and ammonium bicarbonate into the materials, neutralizing the dissolved hydrogen chloride in the system at the temperature of 30-60 ℃ for 1-3 hours, and stopping neutralization when the PH value is 6-8, wherein the reaction formula is as follows:
after neutralization, layering and filtering to obtain the high-boiling-point silicon oil product.
In the layered filtration process, a conventional method may be employed.
The invention is also characterized in that: in the neutralization process, the neutralization temperature of 30-60 ℃ is as follows: the temperature of the system is 30-50 ℃ when the urea is added, 40-60 ℃ when the fluxing agent is added, and 30-50 ℃ when the ammonium bicarbonate is added.
The invention is also characterized in that products with different viscosities, namely different molecular weights, can be obtained by changing the proportion of urea, fluxing agent and ammonium bicarbonate.
The technical indexes of the product are as follows:
appearance: a light yellow to yellow brown transparent liquid without mechanical impurities; viscosity (25 ℃, mm)2(s, not less than): 10.0; refractive index (25 ℃, not less than): 1.4400, respectively; pH value: 6.0-8.0; specific gravity: 0.98～1.10。
The invention is also suitable for producing the monomethyltrimethoxysilane by the monomethyltrichlorosilane and producing the low-boiling silicone oil by the low-boiling-point substances which are by-produced in the process of synthesizing the methylchlorosilane by the direct method.
The invention comprehensively utilizes the organic silicon high-boiling residues, and solves the problem of recycling the high-boiling residues which restrict the further development of organic silicon monomers. The whole production process basically has no energy consumption, does not need a heat supply facility, and can be realized by utilizing the generated heat and the neutralization heat of the reaction of the heat exchanger; the reaction is carried out at normal temperature and normal pressure, and the industrial production is easy to realize; the molecular weight of the product produced by the method can be randomly controlled, and the product performance is stable; the reaction can be carried out in an enamel kettle, and the corrosion effect on equipment is small; the production process has no "three wastes" pollution, and the by-product ammonium chloride can be used as chemical fertilizer. The method also has the advantages of short flow, low production cost, high yield and the like.
Drawings
The attached drawing is a process flow chart of the invention.
Detailed Description
Embodiments of the invention will be described in further detail below with reference to the following drawings:
the main experimental data of examples 1 to 14 are shown in the attached table.
| Serial number | High boiling substance | Methanol | Urea | Fluxing agent | Ammonium bicarbonate | pH value | Viscosity (25 ℃, mm)2/s) | Refractive index |
| 1 | 100 | 50 | 60 | 6.0 | 40.0 | 7.5 | 41 | 1.4065 |
| 2 | 100 | 50 | 60 | 6.0 | 30.0 | 6.0 | 12 | 1.4445 |
| 3 | 100 | 50 | 65 | 7.0 | 35.0 | 7.0 | 20 | 1.4498 |
| 4 | 100 | 50 | 70 | 8.0 | 40.0 | 8.0 | 45 | 1.4664 |
| 5 | 100 | 55 | 60 | 6.0 | 40.0 | 7.5 | 42 | 1.4620 |
| 6 | 100 | 55 | 60 | 6.0 | 30.0 | 6.0 | 17 | 1.4490 |
| 7 | 100 | 55 | 65 | 7.0 | 35.0 | 7.0 | 24 | 1.4510 |
| 8 | 100 | 55 | 70 | 8.0 | 40.0 | 8.0 | 39 | 1.4600 |
| 9 | 100 | 60 | 60 | 6.0 | 40.0 | 7.5 | 40 | 1.4610 |
| 10 | 100 | 60 | 60 | 9.0 | 30.0 | 6.0 | 11 | 1.4435 |
| 11 | 100 | 60 | 65 | 10.0 | 35.0 | 7.0 | 19 | 1.4495 |
| 12 | 100 | 60 | 70 | 12.0 | 40.0 | 8.0 | 43 | 1.4634 |
| 13 | 100 | 50 | 60 | 13.0 | 38.0 | 7.5 | 39 | 1.4610 |
| 14 | 100 | 60 | 70 | 10.0 | 32.0 | 7.0 | 14 | 1.4477 |
Examples 1 to 4
Pumping high-boiling-point substances into an enamel kettle, pumping methanol into a head tank, starting stirring, dripping the methanol in the head tank at the room temperature of 20 ℃, wherein the dripping time is 1 hour, the temperature of the kettle after dripping is 30 ℃, and continuously deacidifying at the temperature (hydrogen chloride gas generated in the dripping process is sent to a water spray tower for absorption through an air draft device) for 3 hours.
Adding urea with the formula amount from a hand hole of a reaction kettle, then adding fluxing agent zinc oxide, and finally adding ammonium bicarbonate for neutralization. The temperature of the process of adding urea and zinc oxide naturally rises, but when the temperature rises to be close to 60 ℃, the feeding speed is slowed down, the temperature of the system is controlled to be lower than 60 ℃, when the adding amount of ammonium bicarbonate is about 80 percent, sampling is started to measure the PH value of an upper oil layer, when the PH value meets the requirement, the neutralization is stopped, and the neutralization time is about 3 hours.
After neutralization, stopping the stirring and air draft device, standing for layering, standing for 1 hour, separating out a lower-layer liquid eutectic substance through a bottom valve sight glass of the reaction kettle, and putting the eutectic substance into a lime pool for continuous neutralization to be neutral; the upper layer is the crude product of the target product.
Transferring the crude product of the target product into a filter tank, and filtering out impurities in the crude product by using a diatomite filter aid to obtain light yellow transparent liquid, namely the target product-high-boiling silicone oil.
Examples 5 to 9
Adding high-boiling-point substances into a kettle, dropwise adding methanol at the room temperature of 25 ℃, wherein the dropwise adding time is 100 minutes, the temperature of the kettle reaches 32 ℃ after the dropwise adding, deacidifying at the temperature (feeding hydrogen chloride gas generated in the dropwise adding process into an acid recovery tank for recovery through a water-ring vacuum pump), wherein the deacidifying time is 150 minutes, and adding urea, zinc oxide serving as a fluxing agent and ammonium bicarbonate serving as the formula amount. Adding urea at a system temperature lower than 50 ℃; adding a fluxing agent, wherein the system temperature is lower than 60 ℃; during the process of adding ammonium bicarbonate, the temperature of the system is higher than 30 ℃. Neutralizing for 2.5 hours, standing for 40 minutes after neutralization, layering, and filtering the crude product of the target product on the upper layer by a diatomite filter aid to obtain a light yellow transparent liquid.
Examples 10 to 12
Adding high-boiling-point substances into a kettle, dropwise adding methanol at room temperature of 20 ℃, wherein the dropwise adding time is 110 minutes, the temperature of the kettle reaches 30 ℃ after the dropwise adding, deacidifying at the temperature (sending hydrogen chloride gas generated in the dropwise adding process into an acid recovery tank through an air draft device for recovery), wherein the deacidifying time is 120 minutes, and adding urea, zinc carbonate and ammonium bicarbonate serving as fluxing agents according to the formula. The urea is added, and the system temperature is lower than 45 ℃; adding a fluxing agent, wherein the system temperature is lower than 55 ℃; during the process of adding ammonium bicarbonate, the temperature of the system is higher than 35 ℃. The neutralization time is 2.5 hours in total, after neutralization, the mixture is kept stand for 50 minutes and then layered, and the crude product of the target product on the upper layer is filtered by a diatomite filter aid to be light yellow transparent liquid.
Examples 13 to 14
Adding high-boiling-point substances into a kettle, dropwise adding methanol at the room temperature of 25 ℃, wherein the dropwise adding time is 120 minutes, the temperature of the kettle reaches 34 ℃ after the dropwise adding, deacidifying at the temperature (hydrogen chloride gas generated in the dropwise adding process is sent into a water spray tower through an air draft device for absorption), and adding urea, fluxing agent zinc chloride and ammonium bicarbonate with the formula amount sequentially, wherein the deacidifying time is 150 minutes. And (3) adding urea, wherein the system temperature is lower than 48 ℃, adding zinc chloride, the system temperature is lower than 60 ℃, adding ammonium bicarbonate, the system temperature is higher than 35 ℃, neutralizing for 3 hours, standing for 50 minutes after neutralization, layering, and filtering the crude product of the target product on the upper layer by using a diatomite filter aid to obtain light yellow transparent liquid.
Claims (9)
1. A preparation method for synthesizing high-boiling silicone oil by using organic silicon high-boiling residues is characterized by comprising the following steps:
the raw materials are proportioned as follows (parts by weight)
50-60 parts of organic silicon high-boiling-point substance 100 methanol and 60-70 parts of urea
30-40 parts of 6-13 parts of ammonium bicarbonate serving as fluxing agent
The preparation process comprises the following steps:
① alcoholysis step, dripping methanol into the organosilicon high-boiling component, and carrying out alcoholysis reaction at normal temperature, wherein the reaction process is as follows:
main reaction:
side reaction:
side reaction:
the methanol dripping time is 1-2 hours, hydrogen chloride gas generated in the dripping reaction process is sent into an acid recovery device through an air draft device for recovery, and deacidification is continued for 2-3 hours after dripping;
② neutralizing the above materials by adding urea, flux and ammonium bicarbonate, neutralizing the dissolved hydrogen chloride in the system at 30-60 deg.C for 1-3 hr, and stopping the neutralization when the pH value is 6-8, wherein the reaction formula is as follows:
after neutralization, layering and filtering to obtain the high-boiling-point silicon oil product.
2. The method according to claim 1, wherein the flux is zinc oxide, zinc chloride or zinc carbonate.
3. The method of claim 2, wherein: when the fluxing agent is zinc oxide, the raw material proportion is6-8 parts by weight.
4. The method of claim 2, wherein: when the fluxing agent is zinc chloride, the raw material proportion is 10-13 parts by weight.
5. The method of claim 2, wherein: when the fluxing agent is zinc carbonate, the raw material proportion is 9-12 parts by weight.
6. The method of claim 1, wherein: in the neutralization process, the neutralization temperature of 30-60 ℃ is as follows: the temperature of the system is 30-50 ℃ when the urea is added, 40-60 ℃ when the fluxing agent is added, and 30-50 ℃ when the ammonium bicarbonate is added.
7. The method of claim 1, wherein: the organic silicon high-boiling residue is a byproduct obtained by synthesizing methyl chlorosilane by a direct method, the boiling range is 80-215 ℃, and the main chain is-Si-Si-, Si-O-Si-or/and Si-CH2-Si-, etc. chlorosilane mixtures.
8. The method of claim 1, wherein: and in the layered filtration, standing for 0.5-1 hour for layering, separating out the lower-layer liquid eutectic, taking out the upper-layer product crude product, and filtering to obtain the finished product.
9. The method of claim 1, wherein: the acid recovery device is a water spray tower and an acid recovery tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410013358 CN1249127C (en) | 2004-06-23 | 2004-06-23 | Process for preparing high boiling silicone oil by using organic high boiling point matter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410013358 CN1249127C (en) | 2004-06-23 | 2004-06-23 | Process for preparing high boiling silicone oil by using organic high boiling point matter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1594400A true CN1594400A (en) | 2005-03-16 |
| CN1249127C CN1249127C (en) | 2006-04-05 |
Family
ID=34662923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410013358 Expired - Fee Related CN1249127C (en) | 2004-06-23 | 2004-06-23 | Process for preparing high boiling silicone oil by using organic high boiling point matter |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1249127C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016383B (en) * | 2007-01-24 | 2011-05-11 | 吉林市凇泰化工有限责任公司 | Method of producing high boiling point silicon oil |
| CN102134256A (en) * | 2011-04-09 | 2011-07-27 | 吉林化工学院 | Method for preparing neutral ethyoxyl high-boiling-point silicone oil by using lower raffinate from ethoxylation of organosilicon high-boiling-point materials |
| CN102134257A (en) * | 2011-04-09 | 2011-07-27 | 吉林化工学院 | Method for treating lower raffinate from methoxylation of organosilicon high-boiling-point materials |
| CN102134320A (en) * | 2011-04-09 | 2011-07-27 | 吉林化工学院 | Preparation method of organic silicon methoxy/ethoxy high boiling silicone oil |
| CN102134258A (en) * | 2011-04-09 | 2011-07-27 | 吉林化工学院 | Method for preparing neutral ethyoxyl high-boiling-point silicone oil by using organosilicon high-boiling-point material as raw material |
| CN101456955B (en) * | 2007-12-14 | 2012-10-10 | 枣阳市康德化工有限公司 | Method for synthesizing high-boiling silicon oil by using organosilicon high-boiling product |
| CN103204992A (en) * | 2013-02-19 | 2013-07-17 | 浙江中天氟硅材料有限公司 | Method for preparing low-viscosity high-boiling silicone oil from raw material of chlorosilane high boiling residue |
| CN105778098A (en) * | 2015-12-25 | 2016-07-20 | 内蒙古神舟硅业有限责任公司 | Method for synthesis of silicone oil by using residual liquid high-boiling substance in polysilicon production |
-
2004
- 2004-06-23 CN CN 200410013358 patent/CN1249127C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016383B (en) * | 2007-01-24 | 2011-05-11 | 吉林市凇泰化工有限责任公司 | Method of producing high boiling point silicon oil |
| CN101456955B (en) * | 2007-12-14 | 2012-10-10 | 枣阳市康德化工有限公司 | Method for synthesizing high-boiling silicon oil by using organosilicon high-boiling product |
| CN102134320A (en) * | 2011-04-09 | 2011-07-27 | 吉林化工学院 | Preparation method of organic silicon methoxy/ethoxy high boiling silicone oil |
| CN102134257A (en) * | 2011-04-09 | 2011-07-27 | 吉林化工学院 | Method for treating lower raffinate from methoxylation of organosilicon high-boiling-point materials |
| CN102134258A (en) * | 2011-04-09 | 2011-07-27 | 吉林化工学院 | Method for preparing neutral ethyoxyl high-boiling-point silicone oil by using organosilicon high-boiling-point material as raw material |
| CN102134320B (en) * | 2011-04-09 | 2012-06-27 | 吉林化工学院 | Preparation method of organic silicon methoxy/ethoxy high boiling silicone oil |
| CN102134256A (en) * | 2011-04-09 | 2011-07-27 | 吉林化工学院 | Method for preparing neutral ethyoxyl high-boiling-point silicone oil by using lower raffinate from ethoxylation of organosilicon high-boiling-point materials |
| CN102134257B (en) * | 2011-04-09 | 2013-07-17 | 吉林化工学院 | Method for treating lower raffinate from methoxylation of organosilicon high-boiling-point materials |
| CN102134256B (en) * | 2011-04-09 | 2013-07-17 | 吉林化工学院 | Method for preparing neutral ethyoxyl high-boiling-point silicone oil by using lower raffinate from ethoxylation of organosilicon high-boiling-point materials |
| CN102134258B (en) * | 2011-04-09 | 2013-07-17 | 吉林化工学院 | Method for preparing neutral ethyoxyl high-boiling-point silicone oil by using organosilicon high-boiling-point material as raw material |
| CN103204992A (en) * | 2013-02-19 | 2013-07-17 | 浙江中天氟硅材料有限公司 | Method for preparing low-viscosity high-boiling silicone oil from raw material of chlorosilane high boiling residue |
| CN103204992B (en) * | 2013-02-19 | 2014-12-24 | 浙江中天氟硅材料有限公司 | Method for preparing low-viscosity high-boiling silicone oil from raw material of chlorosilane high boiling residue |
| CN105778098A (en) * | 2015-12-25 | 2016-07-20 | 内蒙古神舟硅业有限责任公司 | Method for synthesis of silicone oil by using residual liquid high-boiling substance in polysilicon production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1249127C (en) | 2006-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101016383B (en) | Method of producing high boiling point silicon oil | |
| CN109824903B (en) | High-refractive-index boron-containing organic silicon tackifier and preparation method thereof | |
| CN101348498B (en) | Preparation of methyl tributanoximo silane | |
| CN1500083A (en) | Enantioselective synthesis of azetidinone intermediate compounds | |
| CN102516543B (en) | Production method for preparing high-boiling silicone oil by alcoholysis of organosilicon high-boiling components | |
| CN102372733A (en) | Continuous preparation method for methyl trialkoxysilane | |
| CN101824046B (en) | Method for generating dimethyldichlorosilance by utilizing disproportionation reaction | |
| CN109053794B (en) | Trialkoxysilane with thioether bond connected to alpha-carbon and different functional groups based on mercapto-alkene click reaction and preparation method thereof | |
| CN1594400A (en) | Process for preparing high boiling silicone oil by using organic high boiling point matter | |
| CN113999397B (en) | Preparation method and application of low-cost liquid polycarbosilane | |
| CN109569489A (en) | A kind of process units and its preparation process of high boiling point silicon oil | |
| CN103204992B (en) | Method for preparing low-viscosity high-boiling silicone oil from raw material of chlorosilane high boiling residue | |
| CN105801861A (en) | Method for preparing superfine powder silicon resin from organic silicon high-boiling residues | |
| CN101824047A (en) | Method for preparing methyl chlorosilane by cracking organic silicon high boiling point substance | |
| CN102250133B (en) | Method for preparing dimethyl dichlorosilane by using disproportionation method | |
| CN1247598C (en) | Continuous transesterification process for alkoxyorganosilicon compounds | |
| CN108586516B (en) | Preparation method of carbamate alkoxy silane and isocyanate alkoxy silane | |
| CN111100162A (en) | Cyanotrialkoxysilane and preparation method thereof | |
| CN1693307A (en) | Alkyl acyloxy silicane and its preparation process and process for preparing RTV room temp silicon sulfide rubber acetic acid type crosslinking agent | |
| CN105622660B (en) | A kind of secondary aminosilane coupling agent preparation method | |
| CN1166722C (en) | Fluorosilicic phenylene copolymer and its prepn process | |
| CN1301258C (en) | Improved producing process of methyl chlorosilane | |
| CN113637169B (en) | High-quality organic silicon high-boiling hydrolysis oil and preparation method thereof | |
| CN104610337A (en) | VOC emission-free silane coupling agent and synthetic method thereof | |
| CN1174988C (en) | Technique of combination processing organic phosphorus and organosilicon monomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060405 Termination date: 20140623 |
|
| EXPY | Termination of patent right or utility model |