CN105601936A - Method for eliminating residues of polydimethylsilane cracking reaction - Google Patents
Method for eliminating residues of polydimethylsilane cracking reaction Download PDFInfo
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- CN105601936A CN105601936A CN201610018273.8A CN201610018273A CN105601936A CN 105601936 A CN105601936 A CN 105601936A CN 201610018273 A CN201610018273 A CN 201610018273A CN 105601936 A CN105601936 A CN 105601936A
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- reaction vessel
- poly dimethyl
- dimethyl silane
- reaction
- residue
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- 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
- C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
Abstract
The invention provides a method for eliminating residues of PDMS (polydimethylsilane) cracking reaction. The method includes: using an organic solvent of soluble PCS (polycarbosilane) to clean a reaction vessel, then using oxidative acids for cleaning the reaction vessel, and finally using deionized water or distilled water for cleaning the reaction vessel and drying. By the method, the residues of the PDMS cracking reaction can be eliminated quickly and thoroughly, maintenance of reaction equipment is realized while influences of the residues on subsequent reaction processes are reduced, and performance stability and reliability of reaction products are improved.
Description
Technical field
The invention belongs to Polycarbosilane preparing technical field, be specifically related to that a kind of to remove the cracking of poly dimethyl silane anti-Answer the method for residue.
Background technology
Carborundum (SiC) is a kind of high performance ceramic material, can be widely used in high-performance SiC ceramic fibre,The aspects such as ceramic matric composite, ceramic coating, ceramic membrane, foamed ceramics, ceramic. Polycarbosilane(PCS) be the most frequently used precursor legal system precursor for high-performance SiC material, generally by poly dimethyl siliconAlkane (PDMS) makes by cracking rearrangement reaction under high temperature (400-500 DEG C) condition of high voltage. For improvingThe heat-resisting quantity of whole SiC material, non-oxidizability, electromagnetic performance etc., conventionally in the time that cracking is reset by heterogeneous elementComplex compound is incorporated on PCS main chain, obtains containing heterogeneous element Polycarbosilane for example polyaluminocarbosilane (PACS).Heterogeneous element comprises aluminium, iron, titanium, zirconium, cobalt, nickel, boron etc.
Containing heterogeneous element Polycarbosilane normally by poly dimethyl silane (PDMS) at high temperature (400-600 DEG C)Under condition of normal pressure, generate poly-silicon-carbon silane (PSCS) or liquid polysilane (LPCS) by cracking reaction, soAfter it is mixed with containing heterogeneous element complex compound, reaction generation under 400-500 DEG C of condition.
Under poly dimethyl silane (PDMS) high-temperature and high-pressure conditions, prepare Polycarbosilane (PCS) by cracking reaction,And prepare poly-silicon-carbon silane (PSCS) by cracking reaction under poly dimethyl silane (PDMS) high-temperature pressure conditionOr in the process of liquid Polycarbosilane (LPCS), except obtaining target product PCS, PSCS or LPCS,Also can be attached in reaction vessel by residual atrament, be not easy to be removed. This atrament comprise PCS,The mixture of carbon containing, silicon and other material. Along with reaction times increases, this atrament increases gradually, gestureMass-and heat-transfer must affect reaction time, affects reaction process, causes product property unstable.
Therefore, develop a kind of method ten of removing effectively, easily poly dimethyl silane cracking reaction residueDivide important.
Summary of the invention
For the above-mentioned state of the art, the present invention aims to provide a kind of poly dimethyl silane cracking reaction residue of removingMethod, the method is simple, can effectively remove the residue after poly dimethyl silane cracking reaction.
The present invention realizes the technical scheme that above-mentioned technical purpose adopts: a kind ofly remove the cracking of poly dimethyl silaneThe method of reaction residue, is characterized in that: in the reaction vessel after poly dimethyl silane cracking reaction, first addThe organic solvent that enters solvable Polycarbosilane cleans, and then adds oxidizing acid to clean, finally spend fromSub-water or distilled water clean post-drying.
Described poly dimethyl silane cracking reaction residue refers to residual after Pintsch process of poly dimethyl silaneStay thing, include but not limited to the standby poly-silicon-carbon silane (PSCS) of poly dimethyl silane cracking under high-temperature pressure conditionOr the residue of liquid Polycarbosilane (LPCS), and poly dimethyl silane cracking under high-temperature and high-pressure conditionsPrepare the residue of Polycarbosilane (PCS) etc.
The organic solvent of described solvable Polycarbosilane (PCS) include but not limited to benzene,toluene,xylene,One or more mixtures in oxolane, cyclohexane, normal heptane, carbon tetrachloride, chloroform etc.
Described oxidizing acid includes but not limited to that one or more in the concentrated sulfuric acid, red fuming nitric acid (RFNA), perchloric acid etc. are mixedCompound. As preferably, the mass percent of the described concentrated sulfuric acid is 90-98%, and the mass percent of red fuming nitric acid (RFNA) is50-70%, the mass percent of perchloric acid is 60-80%.
As the preferred implementation of one, the method bag of above-mentioned removing poly dimethyl silane cracking reaction residueDraw together following steps:
Step 1: add and can contain intermingle with carbon in the reaction vessel after poly dimethyl silane (PDMS) cracking reactionThe organic solvent of silane (PCS), heating reaction vessel, makes temperature in container reach 10-100 DEG C, is preferably50-80 DEG C, ensureing that liquid in container flows and fully contacts under the condition of residue, keeps 0.1-100 hour,Be preferably 1-10 hour, then shift out the liquid in reaction vessel;
Step 2: add oxidizing acid in reaction vessel, heating reaction vessel, reaches temperature in container30-120 DEG C, is preferably 50-80 DEG C, is ensureing that liquid in container flows and fully contacts under the condition of residue,Keep 0.1-100 hour, be preferably 5-10 hour, then by the liquid shifting out in reaction vessel;
Step 3: add distilled water or washed with de-ionized water reaction vessel in reaction vessel, scavenging period is preferredFor 1-30 minute, after cleaning, shift out the liquid in reaction vessel, then dry reaction vessel, bake out temperature is excellentElect 10-100 DEG C as.
In described step 1 and step 2, ensure mobile can implementation not the limitting of liquid in container, comprise and stirringMix, one or several mixing in vibration, ultrasonic processing etc.
In sum, the invention provides a kind of method of removing poly dimethyl silane cracking reaction residue, shouldMethod is simply easy to realize, and can fast and effeciently remove the residue after poly dimethyl silane cracking reaction, profitCan maintain consersion unit by the method, extend the consersion unit life-span, can reduce described residue to rear simultaneouslyThe impact of continuous reaction process, increases reaction stability and reliability, improves the performance of product.
Brief description of the drawings
Fig. 1 is before cleaning in the embodiment of the present invention 1, after step (1) is cleaned, and clear through step (2)Flask photo after washing.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, it is pointed out that the following stated enforcementExample is intended to be convenient to the understanding of the present invention, and it is not played to any restriction effect.
Embodiment 1:
In the present embodiment, poly dimethyl silane cracking reaction container is 250ml quartz material flask, removes crackingAfter reaction, the method for residue is as follows:
(1) 100ml oxolane is added in described flask, heating flask, makes temperature in flask reach 50 DEG C,Magnetic agitation makes the interior liquid flow of flask and fully contacts residue, stirs 1 hour, then by the liquid in flaskBody is poured out;
(2) be 98% concentrated sulfuric acid 100ml to adding mass percent in flask, heating flask, makes flaskInterior temperature reaches 80 DEG C, and magnetic agitation makes the interior liquid flow of flask and fully contacts residue, stir 2 hours,Then the liquid in flask is poured out;
(3) in flask, add deionized water 250ml to clean flask, clean and poured out flask after 5 minutes,Then heat flask, make temperature in flask reach 100 DEG C, keep 1 hour, flask is dried, and residueAll be eliminated.
Fig. 1 be clean before, through step (1) clean after, and through step (2) clean after photo, canFind out, after cleaning step in the present embodiment cleans, flask is thoroughly cleaned up.
Embodiment 2:
In the present embodiment, poly dimethyl silane cracking reaction container is 20L stainless steel cauldron, removes crackingAfter reaction, the method for residue is as follows:
(1) 10L dimethylbenzene is added in described reactor, heating reactor, reaches reactor temperature80 DEG C, stir and make liquid flow in reactor, stir 5 hours, then the liquid in reactor is poured out;
(2) be 65% red fuming nitric acid (RFNA) 10L to adding mass percent in reactor, heating reactor, makes stillInterior temperature reaches 60 DEG C, stir and make liquid flow in reactor, stirs 5 hours, then by reactorLiquid is poured out;
(3) in reactor, add deionized water 20L cleaning reaction still, after cleaning 10min, poured out anti-Answer still, then heat reactor, make reactor temperature reach 80 DEG C, simultaneously with vavuum pump in reactorVacuumize 3 hours, reactor is dried, and residue is all eliminated.
After the above-mentioned cleaning of this reactor, thoroughly cleaned up.
Above-described embodiment has been described in detail technical scheme of the present invention, is understood that above instituteOnly state as specific embodiments of the invention, be not limited to the present invention, all within the scope of principle of the present invention instituteAny amendment of making, supplement or similar fashion substitutes etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a method of removing poly dimethyl silane cracking reaction residue, is characterized in that: at poly dimethylIn reaction vessel after silane cracking reaction, first add the organic solvent of solvable Polycarbosilane to clean, thenAdd oxidizing acid to clean, finally clean post-drying with deionized water or distilled water.
2. the method for removing poly dimethyl silane cracking reaction residue according to claim 1, its spyLevy and be: described poly dimethyl silane cracking reaction residue comprises that poly dimethyl silane is under high-temperature pressure conditionThe residue of the standby poly-silicon-carbon silane of cracking or liquid Polycarbosilane, and poly dimethyl silane is at HTHP barUnder part, cracking is for the residue of Polycarbosilane.
3. the method for removing poly dimethyl silane cracking reaction residue according to claim 1, its spyLevy and be: the organic solvent of described solvable Polycarbosilane comprises benzene,toluene,xylene, oxolane, hexamethyleneOne or more mixtures in alkane, normal heptane, carbon tetrachloride, chloroform.
4. the method for removing poly dimethyl silane cracking reaction residue according to claim 1, its spyLevy and be: described oxidizing acid comprises one or more mixtures in the concentrated sulfuric acid, red fuming nitric acid (RFNA), perchloric acid.
5. the method for removing poly dimethyl silane cracking reaction residue according to claim 4, its spyLevy and be: the mass percent of the described concentrated sulfuric acid is 90-98%, the mass percent of red fuming nitric acid (RFNA) is 50-70%, heightThe mass percent of chloric acid is 60-80%.
6. according to the removing poly dimethyl silane cracking reaction described in arbitrary claim in claim 1 to 5The method of residue, is characterized in that: comprise the following steps:
Step 1: add the organic of solvable Polycarbosilane in the reaction vessel after poly dimethyl silane cracking reactionSolvent, heating reaction vessel, makes temperature in container reach 10-100 DEG C, is ensureing that liquid in container flows and fillsDivide under the condition of contact residue, keep 0.1-100 hour, then shift out the liquid in reaction vessel;
Step 2: add oxidizing acid in reaction vessel, heating reaction vessel, reaches temperature in container30-120 DEG C, ensureing that liquid in container flows and fully contacts under the condition of residue, keeps 0.1-100 littleTime, then by the liquid shifting out in reaction vessel;
Step 3: add distilled water or washed with de-ionized water reaction vessel in reaction vessel, shift out anti-after cleaningAnswer the liquid in container, then dry reaction vessel.
7. the method for removing poly dimethyl silane cracking reaction residue according to claim 6, its spyLevy and be: in described step 1 and step 2 by one or several guarantees in stirring, vibration, ultrasonic processingLiquid flow in reaction vessel.
8. the method for removing poly dimethyl silane cracking reaction residue according to claim 6, its spyLevy and be: in described step 1, the temperature in reaction vessel is 50-80 DEG C;
As preferably, in described step 1, the retention time is 1-10 hour.
9. the method for removing poly dimethyl silane cracking reaction residue according to claim 6, its spyLevy and be: in described step 2, the temperature in reaction vessel is 50-80 DEG C;
As preferably, in described step 2, the retention time is 5-10 hour.
10. the method for removing poly dimethyl silane cracking reaction residue according to claim 6, its spyLevy and be: in described step 3, scavenging period is 1-30 minute;
As preferably, in described step 3, bake out temperature is 10-100 DEG C.
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| CN201610018273.8A CN105601936B (en) | 2016-01-12 | 2016-01-12 | A kind of method for removing polydimethylsiloxane cracking reaction residue |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050117A (en) * | 2007-03-21 | 2007-10-10 | 中国人民解放军国防科学技术大学 | Method and equipment for preparing precursor body of poly carbon silane ceramics of containing zirconium |
| CN102120822A (en) * | 2011-04-02 | 2011-07-13 | 中国人民解放军国防科学技术大学 | Method for synthetizing polycarbosilane under atmospheric pressure |
| CN103554504A (en) * | 2013-11-21 | 2014-02-05 | 宿迁澳鑫斯新材料有限公司 | Novel method for environmentally and efficiently preparing polycarbosilane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050117A (en) * | 2007-03-21 | 2007-10-10 | 中国人民解放军国防科学技术大学 | Method and equipment for preparing precursor body of poly carbon silane ceramics of containing zirconium |
| CN102120822A (en) * | 2011-04-02 | 2011-07-13 | 中国人民解放军国防科学技术大学 | Method for synthetizing polycarbosilane under atmospheric pressure |
| CN103554504A (en) * | 2013-11-21 | 2014-02-05 | 宿迁澳鑫斯新材料有限公司 | Novel method for environmentally and efficiently preparing polycarbosilane |
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