CN105778098A - Method for synthesis of silicone oil by using residual liquid high-boiling substance in polysilicon production - Google Patents
Method for synthesis of silicone oil by using residual liquid high-boiling substance in polysilicon production Download PDFInfo
- Publication number
- CN105778098A CN105778098A CN201510999143.2A CN201510999143A CN105778098A CN 105778098 A CN105778098 A CN 105778098A CN 201510999143 A CN201510999143 A CN 201510999143A CN 105778098 A CN105778098 A CN 105778098A
- Authority
- CN
- China
- Prior art keywords
- residual liquid
- liquid high
- boiling components
- silicone oil
- production
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a method for synthesis of silicone oil by using a residual liquid high-boiling substance in polysilicon production; in the method, reaction raw material comprises the residual liquid high-boiling substance, methanol or ethanol, and a reaction process includes alcoholysis, analysis, condensation polymerization, neutralization and separation. The reaction conditions are easy to control, the reaction process is simple, and the synthesized silicone oil product has the advantages of stable performance, controllable molecular weight and high oil yield; the method mainly fully recycles the residual liquid high-boiling substance in polysilicon production, solves the problem of backlogging or accumulation of the residual liquid high-boiling substance in polysilicon industry, makes the waste turned into treasure, so as to reduce the production cost of enterprises and reduce environmental pollution problems.
Description
Technical field
The invention belongs to organosilicon material production technical field, the method for residual liquid high-boiling components synthesis silicone oil in specifically a kind of production of polysilicon.
Background technology
Domestic and international production of polysilicon enterprise adopts improved Siemens to produce meeting by-product residual liquid high-boiling components in polysilicon process, continuous expansion along with production scale of enterprise, these residual liquid high-boiling components can constantly gather or overstock, cause the problems such as enterprise's production cost increase and environmental pollution, govern the development of China's polysilicon industry.Component in residual liquid high-boiling components is more complicated, it is containing the chlorosilane of simple substituted radical, polychlorostyrene silane, multi-silane, siloxanes and silicon-carbon alkane etc., structurally convert and relatively difficult in organic separation, and there is strong corrosivity, it is exposed in air under room temperature and has white smoke generation, making people poisoning, being at high temperature exposed to air can catch fire.In reality production of polysilicon, these high-boiling components are easy to form a kind of solid encrusting matter in firing equipment interior surface, and along with the prolongation producing equipment running process, structural material is continuously increased, and affects the stability of equipment operational effect, device.The residual liquid high-boiling components produced in effective recycling polysilicon production process is the important technological problems that current production of polysilicon enterprise solves, and is also one of technological difficulties.
At present, most polysilicon enterprise are adopting cracking process to process residual liquid high-boiling components both at home and abroad, high-boiling components is cracked into chlorosilane monomer mainly through catalyst by cracking process, the technological reaction condition of cracking process is harsh, operating flexibility is big, catalyst price and easily poisoning, the chlorosilane monomer yield of recovery is low, not yet has the technical method adopting the present invention to process polysilicon residual liquid high-boiling components so far in industry.
Summary of the invention
It is an object of the invention to provide a kind of technological process brief, reaction condition is controlled, and properties of product are stable, and molecular weight is controlled, recycles the method for residual liquid high-boiling components synthesis silicone oil in costly production of polysilicon.
Technical scheme is as follows:
A kind of method of residual liquid high-boiling components synthesis silicone oil in production of polysilicon, adopts following steps to carry out:
Reaction raw materials is residual liquid high-boiling components, methanol or ethanol, and course of reaction includes alcoholysis, parsing, polycondensation, neutralization and separation, specifically comprises the following steps that
(1) alcoholysis process
Adding residual liquid high-boiling components 100 parts in reactor, at ambient pressure, be slowly added dropwise methanol or alcoholic solution 20-100 part, the hydrogen chloride gas of generation purges displacement by nitrogen；
(2) resolving
After methanol dropwises, it is warming up to 50-90 DEG C and starts backflow, after refluxing 1-10 hour, remove the hydrogen chloride existed in solution；
(3) polycondensation process
The water being slowly added dropwise 1-20 part in the reactor refluxed reacts further, after dropwising, refluxes 1-8 hour；
(4) N-process
Being cooled to 35-70 DEG C of addition 10-60 part nertralizer and be neutralized reaction, remove the hydrogen chloride dissolved in solution further, after 1-8 hour to be neutralized, when mensuration pH value is between 5-8, stopping neutralizes；
(5) separation process
Standing is layered after placing 1-6 hour, and upper strata is colourless or slightly yellow transparency liquid, and lower floor is pale yellow mixture, is filtered by upper strata oily liquids and obtains target product silicone oil after neutralizing.
Described residual liquid high-boiling components is that polysilicon enterprise produces generation by-product in polysilicon process, mainly includes chlorosilane, polychlorostyrene silane, multi-silane, siloxanes or silicon-carbon alkane, and wherein multi-silane, siloxanes and silicon-carbon alkane are less；
The product of the present invention is alkoxy silane；
Described nertralizer is one or more in carbamide, ammonia, ammonium hydrogen carbonate, sodium bicarbonate or sodium hydroxide etc.；
Described sodium salt is one or more in sodium carbonate, sodium chloride, sodium sulfate；
In described residual liquid high-boiling components, chlorosilane, polychlorostyrene silane and siloxanes ratio are 1:0～0.8:0～0.2；
The product viscosity of the present invention can be changed by the consumption of change reaction temperature, response time and nertralizer.
Compared with prior art, the invention have the advantages that
A, the present invention fully recycle residual liquid high-boiling components in production of polysilicon, solve polysilicon enterprise high-boiling components and overstock or intractable bottleneck problem so that it is turn waste into wealth, reduce production cost, decrease environmental pollution；
B, this synthesis technique short flow, reaction condition is controlled, sintetics stable performance, and molecular weight is controlled, and the hydrogen chloride of generation can fully be recycled, and whole production process thing no waste is discharged；
In c, this synthetic reaction process, use nitrogen to purge continuously and neutralize two parsing hydrogen chloride with nertralizer, be substantially reduced the generation of side reaction；
D, the present invention use alcoholysis, parsing, polycondensation, neutralization and separation process, and fully chlorine atom in elimination high-boiling components, increases methoxyl content, and oil yield reaches more than 70%；
According to the product of technical scheme synthesis, its technical specification is as follows:
This product outward appearance is colourless or slightly yellow transparent oily liquid, mechanical impurity, index of refraction (25 DEG C, be not less than): 1.4180；Viscosity (25 DEG C, mm2/ s, is not less than): 3；Proportion: 0.95～1.10；PH value: 5-8.
Accompanying drawing illustrates:
Fig. 1 is the reaction process schematic diagram with residual liquid high-boiling components synthesis silicone oil.
Detailed description of the invention:
Embodiment 1:
Adding residual liquid high-boiling components 100 parts in reactor, be slowly added dropwise methanol 20 parts at ambient pressure, to promote alcoholysis reaction further, the hydrogen chloride of generation purges displacement continuously by nitrogen, and time for adding is 3h.
Dropwise, be warming up to 50 DEG C and start to reflux 2 hours, remove the hydrogen chloride existed in solution further；
In reactor, it is slowly added to the water of 2 parts, continues backflow 2h, carry out dechlorination atom further.
In reactor, add 20 parts of carbamide, 10 parts of sodium chloride be neutralized reaction, neutralize 2 hours at 35 DEG C, measure pH value in 6 time, stop neutralizing；
It is 2h that reactant mixture moves into stratification in separatory funnel, takes out after supernatant liquid filters neutralization and namely obtains product silicone oil.
Embodiment 2:
Adding residual liquid high-boiling components 100 parts in reactor, be slowly added dropwise methanol 40 parts at ambient pressure, to promote alcoholysis further, the hydrogen chloride of generation purges displacement continuously by nitrogen, and time for adding is 5h.
It is warming up to 65 DEG C to start to reflux 4 hours, removes the hydrogen chloride dissolved in solution further；
In reactor, it is slowly added to the water of 5 parts, continues backflow 4h, carry out dechlorination atom further；
In reactor, add 20 parts of carbamide, 10 parts of ammonium hydrogen carbonate be neutralized reaction, neutralize 4 hours at 45 DEG C, measure pH value in 5 time, stop neutralizing；
It is 6h that reactant mixture moves into stratification in separatory funnel, takes out after supernatant liquid filters neutralization and namely obtains product silicone oil.
Embodiment 3:
Adding residual liquid high-boiling components 100 parts in reactor, be slowly added dropwise methanol 80 parts at ambient pressure, to promote alcoholysis further, the hydrogen chloride of generation purges displacement continuously by nitrogen, and time for adding is 5h.
Dropwise, be warming up to 70 DEG C and start to reflux 6 hours, remove the hydrogen chloride dissolved in solution further；
In reactor, it is slowly added to the distilled water of 10 parts, continues backflow 5h, carry out dechlorination further.
In reactor, add 35 parts of carbamide, 5 parts of sodium bicarbonate, 5 parts of sodium chloride be neutralized reaction, neutralize 6 hours at 60 DEG C, measure pH value in 7 time, stop neutralizing；
It is 8h that reactant mixture moves into stratification in separatory funnel, takes out after supernatant liquid filters and namely obtains product silicone oil.
Embodiment 4:
Adding residual liquid high-boiling components 100 parts in reactor, be slowly added dropwise methanol 50 parts at ambient pressure, to promote alcoholysis further, the hydrogen chloride of generation purges displacement continuously by nitrogen, and time for adding is 4h.
Dropwise, be warming up to 85 DEG C and start to reflux 4 hours, remove the hydrogen chloride dissolved in solution further；
In reactor, it is slowly added to the distilled water of 15 parts, continues backflow 4h, carry out dechlorination further.
In reactor, add 35 parts of sodium bicarbonate, 5 parts of sodium carbonate be neutralized reaction, neutralize 4 hours at 50 DEG C, measure pH value in 6 time, stop neutralizing；
It is 4h that reactant mixture moves into stratification in separatory funnel, takes out after supernatant liquid filters and namely obtains product silicone oil.
Embodiment 5:
Adding residual liquid high-boiling components 100 parts in reactor, be slowly added dropwise methanol 65 parts at ambient pressure, to promote alcoholysis further, the hydrogen chloride of generation purges displacement continuously by nitrogen, and time for adding is 6h.
Dropwise, be warming up to 60 DEG C and start to reflux 3 hours, remove the hydrogen chloride dissolved in solution further；
In reactor, it is slowly added to the water of 10 parts, continues backflow 3h, carry out dechlorination atom further.
In reactor, add 30 parts of ammonium hydrogen carbonate, 5 parts of sodium chloride, 5 parts of sodium carbonate be neutralized reaction, neutralize 3 hours at 45 DEG C, measure pH value in 7 time, stop neutralizing；
It is 5h that reactant mixture moves into stratification in separatory funnel, takes out after supernatant liquid filters and namely obtains product silicone oil.
Claims (5)
1. the method synthesizing silicone oil with residual liquid high-boiling components in production of polysilicon, it is characterised in that: reaction raw materials is residual liquid high-boiling components, methanol or ethanol, and course of reaction includes alcoholysis, parsing, polycondensation, neutralization and separation, specifically comprises the following steps that
(1) alcoholysis process
Adding residual liquid high-boiling components 100 parts in reactor, at ambient pressure, be slowly added dropwise methanol or alcoholic solution 20-100 part, the hydrogen chloride gas of generation purges displacement by nitrogen；
(2) resolving
After methanol dropwises, it is warming up to 50-90 DEG C and starts backflow, after refluxing 1-10 hour, remove the hydrogen chloride existed in solution；
(3) polycondensation process
The water being slowly added dropwise 1-20 part in the reactor refluxed reacts further, after dropwising, refluxes 1-8 hour；
(4) N-process
Being cooled to 35-70 DEG C of addition 10-60 part nertralizer and be neutralized reaction, remove the hydrogen chloride dissolved in solution further, after 1-8 hour to be neutralized, when mensuration pH value is between 5-8, stopping neutralizes；
(5) separation process
Standing is layered after placing 1-6 hour, and upper strata is colourless or slightly yellow transparency liquid, and lower floor is pale yellow mixture, is filtered by upper strata oily liquids and obtains target product silicone oil after neutralizing.
2. the method for residual liquid high-boiling components synthesis silicone oil in production of polysilicon according to claim 1, it is characterized in that, described residual liquid high-boiling components is several in the chlorosilane monomer in polycrystalline silicon production raffinate, polychlorostyrene silane, multi-silane, siloxanes or silicon-carbon alkane, and wherein multi-silane, siloxanes and silicon-carbon alkane are less.
3. the method for residual liquid high-boiling components synthesis silicone oil in production of polysilicon according to claim 1, it is characterised in that described nertralizer is one or more in carbamide, ammonia, ammonium hydrogen carbonate, sodium bicarbonate or sodium hydroxide etc..
4. the method for residual liquid high-boiling components synthesis silicone oil in production of polysilicon according to claim 1, it is characterised in that described sodium salt is one or more in sodium carbonate, sodium chloride, sodium sulfate.
5. the method for residual liquid high-boiling components synthesis silicone oil in production of polysilicon according to claim 1 and 2, it is characterised in that in described residual liquid high-boiling components, chlorosilane, polychlorostyrene silane and siloxanes ratio are 1:0～0.8:0～0.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510999143.2A CN105778098A (en) | 2015-12-25 | 2015-12-25 | Method for synthesis of silicone oil by using residual liquid high-boiling substance in polysilicon production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510999143.2A CN105778098A (en) | 2015-12-25 | 2015-12-25 | Method for synthesis of silicone oil by using residual liquid high-boiling substance in polysilicon production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105778098A true CN105778098A (en) | 2016-07-20 |
Family
ID=56390371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510999143.2A Pending CN105778098A (en) | 2015-12-25 | 2015-12-25 | Method for synthesis of silicone oil by using residual liquid high-boiling substance in polysilicon production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105778098A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114470875A (en) * | 2022-03-10 | 2022-05-13 | 新疆西部合盛硅业有限公司 | Novel efficient high-boiling silicon oil phase separation system and process |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594400A (en) * | 2004-06-23 | 2005-03-16 | 枣阳四海化工有限公司 | Process for preparing high boiling silicone oil by using organic high boiling point matter |
| CN101514244A (en) * | 2009-03-06 | 2009-08-26 | 山东东岳有机硅材料有限公司 | Method for preparing high boiling silicone oil by using organic silicon high boiling substances |
| CN102153752A (en) * | 2010-12-03 | 2011-08-17 | 湖北新四海化工股份有限公司 | Method and device for preparing high-boiling-point silicone oil |
| CN102276839A (en) * | 2010-06-12 | 2011-12-14 | 龚明军 | Method for preparing alkoxyl silicone oil |
| CN102516543A (en) * | 2011-12-07 | 2012-06-27 | 唐山三友硅业有限责任公司 | Production method for preparing high-boiling silicone oil by alcoholysis of organosilicon high-boiling components |
| CN102532547A (en) * | 2011-12-30 | 2012-07-04 | 安徽祥源安全环境科学技术有限公司 | Method for preparing silicon oil from organic silicon high-boiling residues |
| US20130272945A1 (en) * | 2012-04-12 | 2013-10-17 | Korea Institute Of Geoscience And Mineral Resources | Method for Producing Silicon Chloride from Silicon Sludge |
-
2015
- 2015-12-25 CN CN201510999143.2A patent/CN105778098A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594400A (en) * | 2004-06-23 | 2005-03-16 | 枣阳四海化工有限公司 | Process for preparing high boiling silicone oil by using organic high boiling point matter |
| CN101514244A (en) * | 2009-03-06 | 2009-08-26 | 山东东岳有机硅材料有限公司 | Method for preparing high boiling silicone oil by using organic silicon high boiling substances |
| CN102276839A (en) * | 2010-06-12 | 2011-12-14 | 龚明军 | Method for preparing alkoxyl silicone oil |
| CN102153752A (en) * | 2010-12-03 | 2011-08-17 | 湖北新四海化工股份有限公司 | Method and device for preparing high-boiling-point silicone oil |
| CN102516543A (en) * | 2011-12-07 | 2012-06-27 | 唐山三友硅业有限责任公司 | Production method for preparing high-boiling silicone oil by alcoholysis of organosilicon high-boiling components |
| CN102532547A (en) * | 2011-12-30 | 2012-07-04 | 安徽祥源安全环境科学技术有限公司 | Method for preparing silicon oil from organic silicon high-boiling residues |
| US20130272945A1 (en) * | 2012-04-12 | 2013-10-17 | Korea Institute Of Geoscience And Mineral Resources | Method for Producing Silicon Chloride from Silicon Sludge |
Non-Patent Citations (2)
| Title |
|---|
| FU, YUJUN，等: "Catalytic chlorination of methylphenyldichlorosilane with gaseous chlorine to chlorinated methylphenyldichlorosilanes over Lewis acids", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
| 龚家全，等: "用有机硅高沸物生产硅油的方法", 《有机硅材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114470875A (en) * | 2022-03-10 | 2022-05-13 | 新疆西部合盛硅业有限公司 | Novel efficient high-boiling silicon oil phase separation system and process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102372733B (en) | Continuous preparation method for methyl trialkoxysilane | |
| CN102351894B (en) | Preparation method of methylphenyldialkoxysilane | |
| CN102898460B (en) | Technology for preparing double-amino silane and treating by-product | |
| CN105111232B (en) | A kind of preparation technology of MTES | |
| CN109293911A (en) | A kind of preparation method of end silicone based polyether resin | |
| CN105131028A (en) | Preparation method of methyl triethoxysilane | |
| CN106749387B (en) | A kind of preparation method of methyl dimethoxy oxygroup hydrogen silane | |
| CN103396434A (en) | Synthesis method of vinyltrimethoxysilane oligomer | |
| CN103012460A (en) | Alcoholysis process for methyltrimethoxysilane | |
| CN102863465A (en) | Preparation method for methyl phenyl di-alkoxy silane | |
| CN105778098A (en) | Method for synthesis of silicone oil by using residual liquid high-boiling substance in polysilicon production | |
| CN103333200B (en) | A kind of synthetic method of normal-butyl aminopropyltrialkoxysilane | |
| CN104004012A (en) | Method for automation continuous production of halogen alkylation triethoxysilane | |
| CN101503422A (en) | Method for preparing methyl phenyl ring siloxane mixture | |
| CN103601890B (en) | A kind of synthetic method of pectination polysiloxane flax soft finishing agent | |
| CN104292464B (en) | A kind of preparation method of phenyl hydroxy silicon oil | |
| CN104672276A (en) | Synthetic method for preparing dibutyltin dilaurate | |
| CN104804032A (en) | Solvent method synthetic process of Si-75 | |
| CN109651426A (en) | A kind of synthesis technology of methyltrimethoxysilane high-boiling components production waterproofing agent | |
| CN107522731A (en) | A kind of preparation method of MTES | |
| CN102604158A (en) | Synthesis method of mixing ketoxime type cross-linking agent | |
| CN103923319B (en) | The method of high containing hydrogen silicone oil is produced in the solvent-free hydrolysis of monomethyl dichlorosilane | |
| CN105622660A (en) | Preparation method of secondary amido silane coupling agent and preparation method of catalyst thereof | |
| KR20210095631A (en) | Catalyzed Process for the Preparation of Hydrogen from Silylated Derivatives as Hydrogen Carrier Compounds | |
| CN102532547B (en) | Method for preparing silicon oil from organic silicon high-boiling residues |
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: 20160720 |