CN101456955A - Method for synthesizing high-boiling silicon oil by using organosilicon high-boiling product - Google Patents
Method for synthesizing high-boiling silicon oil by using organosilicon high-boiling product Download PDFInfo
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- CN101456955A CN101456955A CNA2007101689257A CN200710168925A CN101456955A CN 101456955 A CN101456955 A CN 101456955A CN A2007101689257 A CNA2007101689257 A CN A2007101689257A CN 200710168925 A CN200710168925 A CN 200710168925A CN 101456955 A CN101456955 A CN 101456955A
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Abstract
A method for synthesizing high-boiler silicon oil by organic silicon high-boiler substances belongs to the technical field of the production technology of high-boiler silicon oil, which mainly solves the problems of excessive use of carbamide, fluxing agent and ammonium hydrogen carbonate of the existing method and comprises the following steps: (1) injecting 700 weight parts of organic silicon high-boiler substances and 350-420 weight parts of methanol with the temperature of 115-128 DEG C into an alcoholysis reaction tower to undergo alcoholysis reaction to discharge chlorine hydride; (2) flowing the reactant into a depickling reaction kettle to depickle for 2-3 hours, and then injecting into a neutralizing reaction kettle; (3) repeating step (1) and step (2); (4) adding 15-16 parts of water, 200-220 parts of carbamide, 30-40 parts of zinc oxide and 100-140 parts of ammonium hydrogen carbonate by weight to the neutralizing reaction kettle to undergo neutralization reaction; (5) stratifying and filtering the neutralized reactant to obtain the high-boiler silicon oil product. The method is characterized by low production cost and high oil yield, which is mainly used for synthesizing high-boiler silicon oil by organic silicon high-boiler substances.
Description
Technical field
The invention belongs to the technical field of producing of high boiling point silicon oil.Be specifically related to a kind of method of synthesizing high boiling point silicon oil by organosilicon high-boiling product.
Background technology
At present, domestic and international many units do a lot of work to comprehensive utilization of high boiling, the method that is adopted mainly contains cracking process, hydrolysis method and alcoholysis method, but these methods all in various degree existence are reacted problems such as difficult control, complex process, product performance instability: as with the single silane of cracking legal system, its severe reaction conditions, dimethyldichlorosilane(DMCS) content is low in the product, and the high boiling material need are first through the distillation processing, otherwise solid residue wherein easily causes poisoning of catalyst; There are deficiencies such as product washing difficulty, quality instability in hydrolysis method; There are problems such as the difficult control of molecular weight, purpose product separation difficulty in existing alcoholysis method.
So, Chinese invention patent has been announced a kind of preparation method's (patent No.: ZL200410013358.4) with the synthetic high boiling point silicon oil of organosilicon high-boiling product, the parts by weight of raw materials proportioning of this patent is: organosilicon high-boiling product 100, methyl alcohol 50～60, urea 60～70, fusing assistant 6～13, bicarbonate of ammonia 30～40; The preparation method is: 1. alcoholysis operation: in organosilicon high-boiling product, drip methyl alcohol, carry out alcoholysis reaction at normal temperatures, methyl alcohol drips 1～2 hour time, the hydrogen chloride gas that produces in the dropwise reaction process is sent into acid-restoring plant by extractor fan and is absorbed, after dropwising, continue depickling 2～3 hours; 2. in and operation: in the above-mentioned material, add urea, fusing assistant and bicarbonate of ammonia, in and dissolved hydrogenchloride in the system, neutral temperature is 30～60 ℃, in and 1～3 hour time, surveying pH value is 6～8 o'clock, stops neutralization, neutralization is finished, and layering, filtration get the high boiling point silicon oil product.Though this patent has solved the deficiency of existing cracking process, hydrolysis method and alcoholysis method, but owing to alcoholysis reaction, neutralization reaction are all carried out in same reactor, what hydrogen chloride gas was got rid of in the alcoholysis reaction process is insufficient, make in the system dissolved hydrogenchloride more, thereby in the neutralization reaction process, need relatively large urea, fusing assistant and bicarbonate of ammonia, have the deficiency that the raw materials for production cost is low inadequately, oil yield is not high enough, oil yield only is 64%.
Summary of the invention
The method that the object of the present invention is to provide a kind of flow process weak point, be easy to suitability for industrialized production, production cost is low and oil yield is high with the synthetic high boiling point silicon oil of organosilicon high-boiling product.
Technical scheme of the present invention is:
A kind of method with the synthetic high boiling point silicon oil of organosilicon high-boiling product is characterized in that comprising following processing step:
1. the first methyl alcohol that organosilicon high-boiling product and 350～420 weight parts, the temperature of 700 weight parts are 115 ℃～128 ℃ evenly injects the alcoholysis reaction tower simultaneously, carry out alcoholysis reaction, reacted 3 hours, simultaneously the hydrogen chloride gas that produces in the reaction process being sent into acid-restoring plant by extractor fan reclaims, reactant flows in the depickling reactor, and reaction process is as follows:
Main reaction :-Si-Cl+CH
3OH →-Si-OCH
3+ HCl ↑,
Side reaction: HCl+CH
3OH → CH
3Cl ↑+H
2O,
Side reaction :-Si-Cl+H
2O →-Si-OH+HCl ↑;
2. with the 1. the reactant that obtains of processing step in the depickling reactor, stir depickling 2～3 hours, the hydrogen chloride gas that continues to produce is sent into acid-restoring plant by extractor fan and is reclaimed, and afterwards reactant is injected the neutralization reaction still;
1. 3. repeat, 2. processing step;
4. after above-mentioned depickling afterreaction thing being injected the neutralization reaction still, the water that adds 15～16 weight parts earlier stirred 30～40 minutes, add the urea of 200～220 weight parts, the zinc oxide of 30～40 weight parts and the bicarbonate of ammonia of 100～140 weight parts again, restir 30～40 minutes, in and depickling afterreaction thing in dissolved hydrogenchloride, neutral temperature is 30～60 ℃, in and 1～3 hour time, surveying pH value is 6～7 o'clock, stops neutralization, and reaction formula is as follows:
(NH
2)
2CO+CH
3OH+3HCl→2NH
4Cl+CH
3Cl↑+CO
2↑
(NH
2)
2CO+H
2O+2HCl→2NH
4Cl+CO
2↑
NH
4HCO
3+HCl→NH
4Cl+H
2O+CO
2↑；
5. with the reactant that obtains after the neutralization reaction through layering, filtration, the high boiling point silicon oil product.
The present invention is owing to adopt the alcoholysis reaction tower, depickling reactor and neutralization reaction still, earlier organosilicon high-boiling product and the methyl alcohol of heating to 115 ℃～128 ℃ are evenly injected the alcoholysis reaction tower simultaneously, carry out alcoholysis reaction, thereby reaction is more abundant, the hydrogen chloride gas that produces in the reaction process is more, the reactant that again the alcoholysis operation is obtained flows into depickling in the depickling reactor, make in the system dissolved hydrogenchloride further overflow and discharged by extractor fan, at last above-mentioned depickling afterreaction thing is injected the neutralization reaction still and add entry, urea, zinc oxide and bicarbonate of ammonia, the reactant that obtains after the neutralization reaction is through layering, filter, get the high boiling point silicon oil product.The present invention is under the situation that adopts the same materials organosilicon high-boiling product, and the consumption of urea, zinc oxide and bicarbonate of ammonia greatly reduces, and only is half of prior art, and cost is reduced greatly, and simultaneously, oil yield further improves, and reaches 75%.The present invention has the advantages that production cost is low, oil yield is high.The present invention is mainly used in the method with the synthetic high boiling point silicon oil of organosilicon high-boiling product.
Embodiment
Embodiment:
Adopt the parts by weight of raw materials proportioning to be:
1400 kilograms of organosilicon high-boiling products, 700 kilograms of methyl alcohol, 210 kilograms in urea,
35 kilograms in zinc oxide, the bicarbonate of ammonia 120 kg;
Its preparation method is:
1. earlier 700 kilograms of organosilicon high-boiling products and 350 kilograms of methyl alcohol are evenly injected the alcoholysis reaction tower simultaneously by volume pump respectively, methyl alcohol is heated to 115 ℃～128 ℃ through vaporizer, carry out alcoholysis reaction, reacted 3 hours, simultaneously the hydrogen chloride gas that produces in the reaction process being sent into acid-restoring plant by extractor fan reclaims, reactant flows into the depickling reactor, and reaction process is as follows:
Main reaction :-Si-Cl+CH
3OH →-Si-OCH
3+ HCl ↑,
Side reaction: HCl+CH
3OH → CH
3Cl ↑+H
2O,
Side reaction :-Si-Cl+H
2O →-Si-OH+HCl ↑;
2. with the 1. the reactant that obtains of processing step in the depickling reactor, stir depickling 2～3 hours, the hydrogen chloride gas that continues to produce is sent into acid-restoring plant by extractor fan and is reclaimed, and afterwards reactant is injected the neutralization reaction still;
1. 3. repeat, 2. processing step;
4. after above-mentioned depickling afterreaction thing being injected the neutralization reaction still, the water that adds 15～16 weight parts earlier stirred 30～40 minutes, add 210 kilograms of urea again, add 35 kilograms of zinc oxide then, add 120 kg bicarbonate of ammonia at last, restir 30～40 minutes, in and depickling afterreaction thing in dissolved hydrogenchloride, add urea, the process temperature of zinc oxide can rise by nature, but when temperature rises near 60 ℃, slow down feed rate, hierarchy of control temperature is lower than 60 ℃, when about 80% left and right sides of bicarbonate of ammonia dosage, begin to take a sample and survey the PH of upper strata oil reservoir, when treating that pH value reaches requirement, stop neutralization, in and about 3 hours of time, reaction formula is as follows:
(NH
2)
2CO+CH
3OH+3HCl→2NH
4Cl+CH
3Cl↑+CO
2↑
(NH
2)
2CO+H
2O+2HCl→2NH
4Cl+CO
2↑
NH
4HCO
3+HCl→NH
4Cl+H
2O+CO
2↑
4. neutralization is finished, standing demix, leave standstill 1 hour after, tell the liquid eutectic of lower floor by neutralization reaction still bottom valve visor, eutectic is put into Calcified pond and is continued to be neutralized into neutrality; The upper strata is purpose product crude product.Change purpose product crude product over to hay tank, leach wherein impurity, obtain flaxen transparent liquid, i.e. purpose product---high boiling point silicon oil by super-cell.
Zinc oxide is fusing assistant, can also adopt zinc carbonate, zinc chloride etc.
The said organosilicon high-boiling product of the present invention is commonly called as high boiling material, the height monomer that boils, and is the by product of direct method synthesizing methyl-chloro-silane, and boiling range is 80～215 ℃, and main chain is-and Si-Si-, Si-O-Si-be or/and Si-CH
2The chlorosilane mixture that-Si-etc. form.
In the layered filtration operation, can adopt ordinary method to carry out.
The technical indicator of this product is as follows:
Outward appearance: yellowish to the tawny transparent liquid, there is not mechanical impurity; Viscosity (25 ℃, mm
2/ s is not less than): 11.0; Refractive index (25 ℃ are not less than): 1.4400; PH value: 6.0～7.0; Proportion: 0.98～1.10.
The present invention also is applicable to monomethyl trichlorosilane production monomethyl Trimethoxy silane, and the low boiling point silicon oil of the low-boiling-point substance production of by-product in the direct method synthesizing methyl-chloro-silane process.
Claims (1)
1, a kind of method with the synthetic high boiling point silicon oil of organosilicon high-boiling product is characterized in that comprising following processing step:
1. the first methyl alcohol that organosilicon high-boiling product and 350～420 weight parts, the temperature of 700 weight parts are 115 ℃～128 ℃ evenly injects the alcoholysis reaction tower simultaneously, carry out alcoholysis reaction, reacted 3 hours, simultaneously the hydrogen chloride gas that produces in the reaction process is sent into acid-restoring plant by extractor fan and reclaim, reactant flows in the depickling reactor;
2. with the 1. the reactant that obtains of processing step in the depickling reactor, stir depickling 2～3 hours, the hydrogen chloride gas that continues to produce is sent into acid-restoring plant by extractor fan and is reclaimed, and afterwards reactant is injected the neutralization reaction still;
1. 3. repeat, 2. processing step;
4. after above-mentioned depickling afterreaction thing being injected the neutralization reaction still, the water that adds 15～16 weight parts earlier stirred 30～40 minutes, add the urea of 200～220 weight parts, the zinc oxide of 30～40 weight parts and the bicarbonate of ammonia of 100～140 weight parts again, restir 30～40 minutes, in and depickling afterreaction thing in dissolved hydrogenchloride, neutral temperature is 30～60 ℃, in and 1～3 hour time, surveying pH value is 6～7 o'clock, stops neutralization;
5. with the reactant that obtains after the neutralization reaction through layering, filtration, the high boiling point silicon oil product.
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|---|---|---|---|
| CN200710168925A CN101456955B (en) | 2007-12-14 | 2007-12-14 | Method for synthesizing high-boiling silicon oil by using organosilicon high-boiling product |
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|---|---|---|---|
| CN200710168925A CN101456955B (en) | 2007-12-14 | 2007-12-14 | Method for synthesizing high-boiling silicon oil by using organosilicon high-boiling product |
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| CN101456955A true CN101456955A (en) | 2009-06-17 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN102276839A (en) * | 2010-06-12 | 2011-12-14 | 龚明军 | Method for preparing alkoxyl silicone oil |
| CN105801861A (en) * | 2016-04-20 | 2016-07-27 | 浙江中天氟硅材料有限公司 | Method for preparing superfine powder silicon resin from organic silicon high-boiling residues |
| CN110540649A (en) * | 2019-10-16 | 2019-12-06 | 哈尔滨工业大学 | Purification method of polyhedral oligomeric silsesquioxane |
| CN111704721A (en) * | 2020-06-29 | 2020-09-25 | 王朝鹏 | Production method of high-boiling silicone oil |
| CN111995754A (en) * | 2020-09-02 | 2020-11-27 | 江西星火狮达科技有限公司 | Diethyl silicone oil and production method thereof |
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| CN1249127C (en) * | 2004-06-23 | 2006-04-05 | 枣阳四海化工有限公司 | Process for preparing high boiling silicone oil by using organic high boiling point matter |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102276839A (en) * | 2010-06-12 | 2011-12-14 | 龚明军 | Method for preparing alkoxyl silicone oil |
| CN102276839B (en) * | 2010-06-12 | 2012-11-07 | 龚明军 | Method for preparing alkoxyl silicone oil |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN105801861A (en) * | 2016-04-20 | 2016-07-27 | 浙江中天氟硅材料有限公司 | Method for preparing superfine powder silicon resin from organic silicon high-boiling residues |
| CN105801861B (en) * | 2016-04-20 | 2019-05-28 | 中天东方氟硅材料有限公司 | The method of organosilicon high-boiling product preparation superfines silicone resin |
| CN110540649A (en) * | 2019-10-16 | 2019-12-06 | 哈尔滨工业大学 | Purification method of polyhedral oligomeric silsesquioxane |
| CN110540649B (en) * | 2019-10-16 | 2022-02-08 | 哈尔滨工业大学 | Purification method of polyhedral oligomeric silsesquioxane |
| CN111704721A (en) * | 2020-06-29 | 2020-09-25 | 王朝鹏 | Production method of high-boiling silicone oil |
| CN111995754A (en) * | 2020-09-02 | 2020-11-27 | 江西星火狮达科技有限公司 | Diethyl silicone oil and production method thereof |
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| CN101456955B (en) | 2012-10-10 |
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Owner name: ZAOZHUANG HUAWEI SILICON + FLUORINE MATERIAL CO., Free format text: FORMER OWNER: ZAOYANG KANGDE CHEMICALS CO., LTD. Effective date: 20131011 |
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Effective date of registration: 20131011 Address after: Jujube City, Hubei province 441200 jujube Ju Lu Patentee after: ZAOYANG HUAWEI FLUOSILICIC MATERIAL Co.,Ltd. Address before: Jujube City, Hubei province 441200 jujube Ju Lu Patentee before: ZAOYANG KANGDE CHEMICALS Co.,Ltd. |
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Denomination of invention: A method for synthesizing high boiling silicone oil from high boiling silicone Effective date of registration: 20221228 Granted publication date: 20121010 Pledgee: Bank of China Limited Xiangyang Branch Pledgor: ZAOYANG HUAWEI FLUOSILICIC MATERIAL Co.,Ltd. Registration number: Y2022980029505 |
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