CN101456955B - 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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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 through organosilicon high-boiling product.
Background technology
At present; Domestic and international many units do a lot of work to comprehensive utilization of high boiling, and the method that is adopted mainly contains cracking process, hydrolysis method and alcoholysis method, but these methods all in various degree existence react 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 high boiling material warp distillation earlier processing, otherwise solid residue wherein is prone to cause 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 preparing 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, and the hydrogen chloride gas that in the dropwise reaction process, produces is sent into acid-restoring plant through extractor fan and 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 system in dissolved hydrogenchloride, neutral temperature is 30～60 ℃; In with 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 reaction kettle; What hydrogen chloride gas was got rid of in the alcoholysis reaction process is insufficient, makes in the system dissolved hydrogenchloride more, thereby in the neutralization reaction process, needs more a large amount of 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 is merely 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 process 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 through extractor fan and reclaim, reactant flows in the depickling reaction kettle, and reaction process is following:
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 process step in the depickling reaction kettle, stir depickling 2～3 hours, continue that the hydrogen chloride gas that produces is sent into acid-restoring plant through extractor fan and reclaim, afterwards reactant is injected the neutralization reaction still;
1. 3. repeat, 2. process 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, added 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 depickling afterreaction thing in dissolved hydrogenchloride, neutral temperature is 30～60 ℃; In with 1～3 hour time; Surveying pH value is 6～7 o'clock, stops neutralization, and reaction formula is following:
(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 alcoholysis reaction tower, depickling reaction kettle 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 reaction kettle, makes 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 adds entry, urea, zinc oxide and bicarbonate of ammonia; The reactant that obtains after the neutralization reaction gets the high boiling point silicon oil product through layering, filtration.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 is merely the half the 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 through volume pump respectively simultaneously; Methyl alcohol is heated to 115 ℃～128 ℃ through evaporator; Carry out alcoholysis reaction, reacted 3 hours, simultaneously the hydrogen chloride gas that produces in the reaction process is sent into acid-restoring plant through extractor fan and reclaim; Reactant flows into the depickling reaction kettle, and reaction process is following:
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 process step in the depickling reaction kettle, stir depickling 2～3 hours, continue that the hydrogen chloride gas that produces is sent into acid-restoring plant through extractor fan and reclaim, afterwards reactant is injected the neutralization reaction still;
1. 3. repeat, 2. process 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, added 210 kilograms of urea again, added 35 kilograms of zinc oxide then; Add 120 kg bicarbonate of ammonia at last, restir 30～40 minutes, in depickling afterreaction thing in dissolved hydrogenchloride, the process temperature that adds urea, zinc oxide can nature rises; 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 the neutralization, in about 3 hours of time, reaction formula is following:
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 through 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 bullion.Change purpose product bullion over to hay tank, leach impurity wherein, obtain flaxen transparent liquid, be i.e. purpose product---high boiling point silicon oil through 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 following:
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. method with the synthetic high boiling point silicon oil of organosilicon high-boiling product is characterized in that comprising following process 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 through extractor fan and reclaim, reactant flows in the depickling reaction kettle;
2. with the 1. the reactant that obtains of process step in the depickling reaction kettle, stir depickling 2～3 hours, continue that the hydrogen chloride gas that produces is sent into acid-restoring plant through extractor fan and reclaim, afterwards reactant is injected the neutralization reaction still;
1. 3. repeat, 2. process 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, added 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 with depickling afterreaction thing in dissolved hydrogenchloride, neutral temperature is 30～60 ℃, in 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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| CN101456955B true CN101456955B (en) | 2012-10-10 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (1)
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|---|---|---|---|---|
| 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 |
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| 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 |
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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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