CN105085921A - Method for preparing methyl hydrogen silicone oil from organic silicon by-product - Google Patents
Method for preparing methyl hydrogen silicone oil from organic silicon by-product Download PDFInfo
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- CN105085921A CN105085921A CN201510508540.5A CN201510508540A CN105085921A CN 105085921 A CN105085921 A CN 105085921A CN 201510508540 A CN201510508540 A CN 201510508540A CN 105085921 A CN105085921 A CN 105085921A
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- methyl hydrogen
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- polysiloxane fluid
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Abstract
The invention relates to a method for preparing methyl hydrogen silicone oil from an organic silicon by-product. The method comprises the steps of carrying out cohydrolysis reaction under certain conditions by virtue of the organic silicon by-product, namely dichloromethylsilane, an end-capping agent, namely chlorotrimethylsilane and recycled washing dilute acid, carrying out back flushing by virtue of compressed air so as to remove hydrogen chloride produced during hydrolysis, standing for layering after the reaction is finished, carrying out washing deacidification on an upper solution for multiple times, and carrying out neutralization, filtration and devolatiligation procedures on products, so as to obtain finished methyl hydrogen silicone oil. Practices prove that methyl hydrogen silicone oil prepared by virtue of the method has controllable viscosity and stable quality and is easy to industrialize, and the comprehensive utilization value of the organic silicon by-product, namely dichloromethylsilane is greatly increased.
Description
Technical field
The invention belongs to organic silicon byproduct production technical field, be specifically related to a kind of method utilizing organic silicon byproduct monomethyl dichlorosilane to prepare Methyl Hydrogen Polysiloxane Fluid.
Background technology
Along with silicone industry develops rapidly, organosilicon chlorosilane monomer output is also increasing, and estimate current year Mo, silicone industry in China monomer manufacturing enterprise aggregated capacity is about 2500kt/a.Monomethyl dichlorosilane is one of by product of organosilicon chlorosilane monomer production, and account for monomer capacity about 1.5%, boiling point only 41.1 DEG C under normal pressure, limits of explosion scope is 6 ~ 55%, the too high easy generation vaporization phenomenon of summer temp, causes security incident; This material inside, containing Si-Cl and active Si-H key, produces a large amount of acid mist after contact damp atmosphere, and then causes secondary accident, therefore, from saving production cost and the analysis of safety and environmental protection aspect, is all necessary to fully utilize this material.
At present, domestic and international organosilicon enterprise great majority utilize monomethyl dichlorosilane to prepare Methyl Hydrogen Polysiloxane Fluid, are mainly divided into solvent method and solventless method.Wherein solvent method is prepared Methyl Hydrogen Polysiloxane Fluid and is not only needed a large amount of toxic organic solvents, as benzene, toluene etc., and finished product exist solvent odor, storage time short, easily return the defects such as acid, can not use in high-end product.Solventless method can avoid the various deficiencies of solvent method product, can production higher gears product, and meet high-end user demand, be conducive to the cultivation of high-end market, potential market capacity is huge.Chinese patent CN102643428A provides a kind of method that solventless method produces Methyl Hydrogen Polysiloxane Fluid, after monomethyl dichlorosilane and tri-methyl-chlorosilane mixing, in instillation hydrolytic reaction pot, control reaction process by controlled hydrolysis temperature and material dropping speed, hydrolysate obtains the Methyl Hydrogen Polysiloxane Fluid refined after centrifugation, filtration, de-low three-procedure.Solvent-free consumption in the method production process, decreases Product processing treatment process, improves product quality; Adopt centrifugal method to be separated thick product deacidification, shorten life cycle of the product, but, because operating environment is harsh,
The centrifugation apparatus adopted is expensive, and separating effect need the use that the factors such as raising further limit this technology.Chinese patent CN102030905A describes the method that another solventless method prepares Methyl Hydrogen Polysiloxane Fluid, reactor is added by monomethyl dichlorosilane, tri-methyl-chlorosilane, inorganic salt solution hydrolysis is dripped under stirring with certain speed, reacted rear stratification and obtained crude containing hydrogen silicone oil, then through neutralization, de-low after obtain refining Methyl Hydrogen Polysiloxane Fluid.The method processing unit is simple, investment cost is low, but, due to monomethyl dichlorosilane and tri-methyl-chlorosilane hydrolysis rate inconsistent, mixing unevenly will directly affect hydrolysis quality, and then affect product quality, in addition, stirring apparatus for reaction kettle trim under strong acidic environment very easily the factor such as damage also limit the use of this technology.
Summary of the invention
The object of the invention is to the shortcoming overcoming above-mentioned prior art, a kind of method utilizing monomethyl dichlorosilane to prepare Methyl Hydrogen Polysiloxane Fluid is provided.
The method utilizing monomethyl dichlorosilane to prepare Methyl Hydrogen Polysiloxane Fluid provided by the invention comprises the steps:
(A) the washing dilute acid soln of recovery is added enamel reaction still, open blowback pressurized air at the bottom of reactor refrigerating unit and still;
(B) in proportion monomethyl dichlorosilane, end-capping reagent tri-methyl-chlorosilane are added drop-wise in reactor after static mixer mixing, control temperature of reaction kettle at-5-45 DEG C, wherein: monomethyl dichlorosilane and tri-methyl-chlorosilane mass ratio are 1:0.05 ~ 0.005;
(C), after hydrolysis reaction completes, after standing for hydrolysate feeding header tank is left standstill 30-60min, namely the concentrated hydrochloric acid of discharging lower floor 25 ~ 31% obtains crude containing hydrogen silicone oil, wherein: the whole export trade of lower floor's concentrated hydrochloric acid;
(D) repeatedly pass into appropriate process water washing crude containing hydrogen silicone oil, reclaim dilute hydrochloric acid solution that washing produces and all for the washing diluted acid in step (A).
(E) wash the Methyl Hydrogen Polysiloxane Fluid after depickling again through in alkaline matter and after, enter the filtration unit removal of impurity.
(F) after de-low, Methyl Hydrogen Polysiloxane Fluid finished product is namely obtained from strainer out Methyl Hydrogen Polysiloxane Fluid, wherein: de-low system vacuum: 0.09-0.01MPa, temperature: 110 ~ 125 DEG C.
The present invention compared with the existing technology its advantage is:
1, adopt static mixer to mix reaction mass and end-capping reagent in advance, can make whole hydrolysis reaction more steadily, hydrolysis effect is more excellent;
2, adopt cheap pressurized air blowback reaction soln, take the hydrogen chloride gas that a large amount of hydrolysis reaction produces out of, decrease the heat of the water-soluble release of hydrogen chloride gas, reduce the consumption of general facilities cold; A large amount of hydrogen chloride gas is reduced the concentration of hydrochloric acid remained in silicone oil by the system of taking out of, decrease neutralizing agent usage quantity; Air blowback causes hydrating solution internal disturbance, and alternative stirring apparatus for reaction kettle, reduces industrial production cost;
3, adopt process water repeatedly to wash the inner hydrochloric acid of crude containing hydrogen silicone oil solution removal, decrease the solid matters such as the salt of follow-up neutralizing agent usage quantity and reaction generation, and then alleviate filtration unit load; By the diluted acid water fully recovering that washing produces, alleviate the effluent pressure of enterprise, greatly reduce the industrial production cost of product.
Embodiment
Embodiment 1
In enamel reaction still, add the washing sour water of recovery, open blowback pressurized air at the bottom of reactor refrigerating unit and still; 1000kg monomethyl dichlorosilane, 10kg tri-methyl-chlorosilane are dropped to reactor after static mixer mixing, maintains temperature in the kettle at 15 ± 5 DEG C; After hydrolysis reaction completes, hydrolysate is delivered to standing header tank, standing 30min isolates lower floor's sour water, obtains crude containing hydrogen silicone oil; After technique water washing crude containing hydrogen silicone oil 3 times, being neutralized to pH value with sodium bicarbonate is again about 6-7, filter, and low molecule in silicone oil is removed under vacuum tightness 80 ± 5KPa, temperature 120 ± 5 DEG C of environment, after 3h Methyl Hydrogen Polysiloxane Fluid finished product, wherein: hydrogen content: 1.58%, refractive index (25 DEG C): 1.4016, viscosity (25 DEG C, mm
2/ s): 30, proportion: 0.9956, volatile matter: 2.536%.
Embodiment 2
Other implementation condition as 1, when end-capping reagent tri-methyl-chlorosilane is 20kg, gained Methyl Hydrogen Polysiloxane Fluid
Hydrogen content: 1.55%, refractive index (25 DEG C): 1.4048, viscosity (25 DEG C, mm
2/ s): 22, proportion: 0.9945, volatile matter: 2.584%.
Embodiment 3
Other implementation condition as 1, when end-capping reagent tri-methyl-chlorosilane is 5kg, gained Methyl Hydrogen Polysiloxane Fluid hydrogen content: 1.61%, refractive index (25 DEG C): 1.4021, viscosity (25 DEG C, mm
2/ s): 35, proportion: 0.9949, volatile matter: 2.576%.
Embodiment 4
Other implementation condition as 1, when adopt sodium carbonate be neutralizing agent time, gained Methyl Hydrogen Polysiloxane Fluid hydrogen content: 1.56%, refractive index (25 DEG C): 1.4075, viscosity (25 DEG C, mm
2/ s): 37, proportion: 0.9959, volatile matter: 2.539%.
Embodiment 5
Other implementation condition as 1, when adopt ammonia be neutralizing agent time, gained Methyl Hydrogen Polysiloxane Fluid hydrogen content: 1.55%, refractive index (25 DEG C): 1.4087, viscosity (25 DEG C, mm2/s): 40, proportion: 0.9963, volatile matter: 2.541%.
Claims (6)
1. utilize organic silicon byproduct to prepare a method for Methyl Hydrogen Polysiloxane Fluid, it is characterized in that comprising the steps:
(A) the washing dilute acid soln of recovery is added enamel reaction still, open blowback pressurized air at the bottom of reactor refrigerating unit and still;
(B) in proportion organic silicon byproduct monomethyl dichlorosilane and end-capping reagent tri-methyl-chlorosilane are added drop-wise in reactor the reaction that is hydrolyzed after static mixer mixing, control reactor temperature, pressure;
(C) after hydrolysis reaction completes, product all delivers to standing header tank stratification, obtains rough acid Methyl Hydrogen Polysiloxane Fluid after repeatedly washing upper strata silicone oil, collects the dilute hydrochloric acid solution that washing produces;
(D) rough acid Methyl Hydrogen Polysiloxane Fluid through neutralization, filter, de-low after namely obtain Methyl Hydrogen Polysiloxane Fluid finished product.
2. the method preparing Methyl Hydrogen Polysiloxane Fluid according to claim 1, is characterized in that: in step (A), compressed air pressure is 0.3-1.0MPa.
3. the method utilizing organic silicon byproduct to prepare Methyl Hydrogen Polysiloxane Fluid according to claim 1, it is characterized in that: in step (B), monomethyl dichlorosilane and tri-methyl-chlorosilane mass ratio are 1:0.05-0.005, hydrolysising reacting temperature controls at-5-45 DEG C, and reaction pressure controls at 0-0.3MPa.
4. the method utilizing organic silicon byproduct to prepare Methyl Hydrogen Polysiloxane Fluid according to claim 1, is characterized in that: in step (C), washing times is 1-5 time, and the washing dilute acid soln of collection is all for the washing diluted acid in step (A).
5. the method utilizing organic silicon byproduct to prepare Methyl Hydrogen Polysiloxane Fluid according to claim 1, is characterized in that: in step (D), neutralizing agent is ammonia, sodium bicarbonate, sodium carbonate.
6. the method utilizing organic silicon byproduct to prepare Methyl Hydrogen Polysiloxane Fluid according to claim 1, is characterized in that: in step (D), de-low system vacuum is 0.09-0.01MPa, temperature is 110 ~ 125 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603230A (en) * | 2017-08-25 | 2018-01-19 | 山东东岳有机硅材料有限公司 | Silicon rubber prepared using organosilicon low boiling hydrolysate and preparation method thereof |
| CN113307974A (en) * | 2021-06-21 | 2021-08-27 | 江西蓝星星火有机硅有限公司 | Method for rapidly recovering hydrogen-containing silicone oil in acid |
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| CN102030905A (en) * | 2010-12-06 | 2011-04-27 | 唐山三友硅业有限责任公司 | Method for preparing solvent-free high hydrogen containing silicone oil |
| CN102408566A (en) * | 2011-10-10 | 2012-04-11 | 衢州瑞力杰化工有限公司 | Production method of methyl hydrogen-containing silicone oil |
| CN102643428A (en) * | 2012-04-27 | 2012-08-22 | 泸州北方化学工业有限公司 | Method for preparing methyl hydrogen polysiloxane oil |
| CN103923319A (en) * | 2014-04-08 | 2014-07-16 | 吉林华丰有机硅有限公司 | Method for producing silicone oil with high hydrogen content by methyldichlorosilae through solvent-free hydrolysis |
| CN104140532A (en) * | 2014-07-30 | 2014-11-12 | 成都博达爱福科技有限公司 | Solvent-free process method for continuously producing methyl hydrogen silicone oil |
| CN104193997A (en) * | 2014-08-21 | 2014-12-10 | 湖北兴发化工集团股份有限公司 | Method and device for preparing high-boiling silicon oil |
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- 2015-08-19 CN CN201510508540.5A patent/CN105085921B/en active Active
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| CN102030905A (en) * | 2010-12-06 | 2011-04-27 | 唐山三友硅业有限责任公司 | Method for preparing solvent-free high hydrogen containing silicone oil |
| CN102408566A (en) * | 2011-10-10 | 2012-04-11 | 衢州瑞力杰化工有限公司 | Production method of methyl hydrogen-containing silicone oil |
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| CN103923319A (en) * | 2014-04-08 | 2014-07-16 | 吉林华丰有机硅有限公司 | Method for producing silicone oil with high hydrogen content by methyldichlorosilae through solvent-free hydrolysis |
| CN104140532A (en) * | 2014-07-30 | 2014-11-12 | 成都博达爱福科技有限公司 | Solvent-free process method for continuously producing methyl hydrogen silicone oil |
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| 张丹丹，陈海平，苗刚: "三甲基氯硅烷水解合成六甲基二硅氧烷的研究", 《有机硅材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603230A (en) * | 2017-08-25 | 2018-01-19 | 山东东岳有机硅材料有限公司 | Silicon rubber prepared using organosilicon low boiling hydrolysate and preparation method thereof |
| CN113307974A (en) * | 2021-06-21 | 2021-08-27 | 江西蓝星星火有机硅有限公司 | Method for rapidly recovering hydrogen-containing silicone oil in acid |
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| CN105085921B (en) | 2018-09-07 |
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Address after: 443007 No. 66-2 Ting Ting Road, Ting Ting District, Yichang, Hubei Patentee after: Hubei Xingrui silicon material Co., Ltd. Address before: 443006 No. 29 Changjiang Road, Ting Ting District, Yichang, Hubei Patentee before: HUBEI XINGRUI CHEMICAL CO., LTD. |
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