CN102532547B - Method for preparing silicon oil from organic silicon high-boiling residues - Google Patents
Method for preparing silicon oil from organic silicon high-boiling residues Download PDFInfo
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- CN102532547B CN102532547B CN201110457249.1A CN201110457249A CN102532547B CN 102532547 B CN102532547 B CN 102532547B CN 201110457249 A CN201110457249 A CN 201110457249A CN 102532547 B CN102532547 B CN 102532547B
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Abstract
The invention discloses a method for preparing silicon oil from organic silicon high-boiling residues. The preparation method comprises the following process steps of: (1) adding organic silicon high-boiling residues into an alcoholysis reaction kettle, dropwise adding a mixed solution of ethanol and a catalyst into the alcoholysis reaction kettle to obtain a reaction mixture, reflowing at the temperature of 60-70 DEG C, exhausting chlorine hydride dissolved into the reaction mixture out of the alcoholysis reaction kettle to obtain a first reaction material into which chlorine hydride is dissolved, and continuously introducing nitrogen; and (2) putting the first reaction material into a neutralizing reaction kettle, adding urea and a latent solvent into the neutralizing reaction kettle, uniformly stirring, adding ammonium hydrogen carbonate into the reaction kettle, stirring, continuously neutralizing the chlorine hydride dissolved into the first reaction material to obtain a second reaction material of which pH is neutral, and filtering to obtain silicon oil. The silicon oil prepared with the method has stable performance and good quality.
Description
Technical field
The present invention relates to a kind of method of being prepared silicone oil by organosilicon high-boiling product.
Background technology
At present, generally adopt direct method to produce methyl chlorosilane monomer both at home and abroad, in direct method, produce in the process of methyl chlorosilane monomer, can produce 3～8% organosilicon high-boiling product.
Organosilicon high-boiling product is to take Si-Si, Si-C-Si to be more than 30 kind of main silane mixture, under normal temperature and pressure its be a kind of black, with irritating smell, there is the mixing liquid of strong corrosion, density is about 1.13g/cm
3, 80～215 ℃ of boiling ranges.
In recent years, along with developing rapidly of silicone industry in China industry, the output of methyl chlorosilane monomer is increasing, has also produced a large amount of organosilicon high-boiling products thereupon.Because organosilicon high-boiling product is difficult to make valuable organochlorosilane by simple method, therefore, the commercial value of organosilicon high-boiling product is always lower, overstocks in a large number, has both caused serious environmental issue and potential safety hazard, wastes again resource.Therefore the further developing of comprehensive development and utilization ，Dui China organosilicon industry of high boiling material has positive effect.
The method of comprehensive utilization of organosilicon high-boiling product comprises: utilize high boiling material to prepare single silane, silicone oil, waterproofing agent of organosilicon, silicone antifoam agent, pottery, silicone resin etc.In recycling the whole bag of tricks of high boiling material, utilize high boiling material to prepare silicone oil and waterproofing agent of organosilicon is more a kind of method of application at present.This method technique is fairly simple, easy to operate.
, there is following defect in the existing method of being prepared silicone oil by organosilicon high-boiling product:
1) adopt normal temperature alcoholysis, be dissolved in that hydrogenchloride in reaction mixture can not be discharged in time and the carrying out that aggravate side reaction, the alcoholysis reaction time is long;
2) adopt single methyl alcohol to carry out alcoholysis reaction, chlorine atom can not be substituted completely on the one hand, make in silicone oil that chlorine dose increases, of poor quality, cost is high, viscosity is uncontrollable, methyl alcohol and hydrogenchloride are very easy to reaction on the other hand, generate water and methyl chloride, and the generation of water impels hydrolyzing chlorosilane, cause the yield of silicone oil low;
3) adopt zinc oxide or the hydrochloride of zinc or the carbonate of zinc as solubility promoter, can in silicone oil, introduce the impurity such as zinc, affect the quality of silicone oil.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of being prepared silicone oil by organosilicon high-boiling product, the silicone oil that adopts present method to prepare, stable performance, better quality.
For solving the problems of the technologies described above, the invention provides a kind of method of being prepared silicone oil by organosilicon high-boiling product, it comprises following processing step:
1) at the temperature of 56～59 ℃, the organosilicon high-boiling product of 100 weight parts is added in alcoholysis reaction still, in alcoholysis reaction still, slowly drip the ethanol of 20～70 weight parts and the mixed solution of 10～20 weight part catalyzer again, catalyzer is sodium ethylate, when being added drop-wise to half weight of described mixed solution, alcoholysis reaction still is heated, Heating temperature is 50～70 ℃, the dropping total time of described mixed solution is 1～3 hour, after dropwising, obtain reaction mixture, then at 60～70 ℃ of temperature, reflux, the hydrogenchloride that makes to be dissolved in reaction mixture is overflowed from alcoholysis reaction still, must be dissolved with the first reaction mass of hydrogenchloride, in reaction process, continuing to pass into temperature is 50～70 ℃, flow is the nitrogen of 1～5L/min,
2) the first reaction mass is put into neutralization reaction still, in neutralization reaction still, add the urea of 10～20 weight parts, the solubility promoter of 10～20 weight parts, solubility promoter is ethanol, after stirring, then add the bicarbonate of ammonia of 10～30 weight parts and stir in neutralization reaction still, to continue neutralization, being dissolved in the hydrogenchloride in the first reaction mass, neutral temperature is 30～70 ℃, in and the time be 1～3 hour, obtain pH for the second neutral reaction mass, after filtration silicone oil.
1) chemical equation in step is:
Main reaction :-Si-Cl+CH
3cH
2oH →-Si-OCH
2cH
3+ HCl ↑
-Si-Cl+CH
3CH
2ONa→-Si-OCH
2CH
3+NaCl
Side reaction: HCl+CH
3cH
2oH → CH
3cH
2cl ↑+H
2o
Side reaction :-Si-Cl+H
2o →-Si-OH+HCl ↑
2) chemical equation in step is:
(NH
2)
2CO+CH
3CH
2OH+3HCl→2NH
4Cl+CH
3CH
2Cl↑+CO
2↑
(NH
2)
2CO+H
2O+2HCl→2NH
4Cl+CO
2↑
NH
4HCO
3+HCl→NH
4Cl+H
2O+CO
2↑
For preparation method of the present invention:
1, in alcoholysis reaction, adopt ethanol as raw material, ethanol is relatively gentle with reacting of hydrogenchloride, avoids impelling hydrolyzing chlorosilane because of the water that side reaction generates fast, thereby improves oil yield;
2, in alcoholysis reaction, add sodium ethylate catalyzer, increased the nucleophilie nucleus ability of oxyethyl group, improved the ability that replaces chlorine atom, and sodium ion can form sodium-chlor with chlorion, make content reduction (chlorinity that is silicone oil is lower), the molecular weight of hydrogenchloride in silicone oil controlled;
3, in neutralization reaction, adopt ethanol as solubility promoter, avoid introducing the impurity such as zinc in silicone oil, improved the Performance and quality of silicone oil.
Therefore, the silicone oil that adopts present method to prepare, stable performance, better quality.
The silicone oil that preparation method of the present invention makes, its technical indicator is as follows:
Outward appearance is yellowish to tawny transparent liquid, machinery-free impurity, and viscosity is not less than 10.0mm
2/ s (25 ℃), refractive index is not less than 1.44 (25 ℃), and pH value is 6.0～7.0, density 0.98～1.10g/ml.
In preparation method of the present invention:
1) hydrogen chloride gas of overflowing from alcoholysis reaction still in step adopts the two-stage spray equipment of series connection to reclaim, and wherein the flow of one-level spray water is 2L/min, and the flow of secondary spray water is 0.5L/min, and the pressure in the spray equipment of the two poles of the earth is all 0.5MPa.
Embodiment
Below by specific embodiment, the invention will be further described, but be not limited to this.
Embodiment 1
A method of being prepared silicone oil by organosilicon high-boiling product, comprises following processing step:
1) at the temperature of 56～59 ℃, the organosilicon high-boiling product of 100 weight parts is added in alcoholysis reaction still, in alcoholysis reaction still, slowly drip the ethanol of 50 weight parts and the mixed solution of 12 weight part catalyzer sodium ethylates again, when being added drop-wise to half weight of described mixed solution, alcoholysis reaction still is heated, Heating temperature is 50 ℃, the dropping total time of described mixed solution is 2 hours, after dropwising, obtain reaction mixture, then at 60 ℃ of temperature, reflux, the hydrogenchloride that makes to be dissolved in reaction mixture is overflowed from alcoholysis reaction still, must be dissolved with the first reaction mass of hydrogenchloride, and to continue to pass into temperature to alcoholysis reaction still and series connection two-stage spray-absorption device be 50 ℃, flow is the nitrogen of 2L/min, the hydrogen chloride gas of overflowing from alcoholysis reaction still adopts the two-stage spray equipment of series connection to reclaim, and wherein the flow of one-level spray water is 2L/min, and the flow of secondary spray water is 0.5L/min, and the pressure in the spray equipment of the two poles of the earth is all 0.5MPa.
2) the first reaction mass is put into neutralization reaction still, to the urea that adds 10 weight parts in neutralization reaction still, the solubility promoter of 10 weight parts, solubility promoter is ethanol, after stirring, in neutralization reaction still, add the bicarbonate of ammonia of 20 weight parts and stir again, to continue neutralization, be dissolved in the hydrogenchloride in the first reaction mass, neutral temperature is 40 ℃, in and the time be 2 hours, after neutralization, stop stirring, stratification, separate thick product, obtaining pH is the second reaction mass neutral and upper strata in neutralization reaction still, obtain after filtration the faint yellow transparent silicone oil of 87.6 weight parts, its viscosity 16.23mm
2/ s (25 ℃), refractive index 1.4501 (25 ℃).
The concrete technology step of embodiment 2～10 is identical with embodiment 1, but processing parameter is different, and concrete data are in Table 1.
Claims (2)
1. by organosilicon high-boiling product, prepared a method for silicone oil, comprise following processing step:
1) at the temperature of 56～59 ℃, the organosilicon high-boiling product of 100 weight parts is added in alcoholysis reaction still, in alcoholysis reaction still, slowly drip the ethanol of 20～70 weight parts and the mixed solution of 10～20 weight part catalyzer again, catalyzer is sodium ethylate, when being added drop-wise to half weight of described mixed solution, alcoholysis reaction still is heated, Heating temperature is 50～70 ℃, the dropping total time of described mixed solution is 1～3 hour, after dropwising, obtain reaction mixture, then at 60～70 ℃ of temperature, reflux, the hydrogenchloride that makes to be dissolved in reaction mixture is overflowed from alcoholysis reaction still, must be dissolved with the first reaction mass of hydrogenchloride, in reaction process, continuing to pass into temperature is 50～70 ℃, flow is the nitrogen of 1～5L/min,
2) the first reaction mass is put into neutralization reaction still, in neutralization reaction still, add the urea of 10～20 weight parts, the solubility promoter of 10～20 weight parts, solubility promoter is ethanol, after stirring, then add the bicarbonate of ammonia of 10～30 weight parts and stir in neutralization reaction still, to continue neutralization, being dissolved in the hydrogenchloride in the first reaction mass, neutral temperature is 30～70 ℃, in and the time be 1～3 hour, obtain pH for the second neutral reaction mass, after filtration silicone oil.
2. according to preparing the method for silicone oil by organosilicon high-boiling product described in claim 1, it is characterized in that:
1) hydrogen chloride gas of overflowing from alcoholysis reaction still in step adopts the two-stage spray equipment of series connection to reclaim, wherein the flow of one-level spray water is 2L/min, the flow of secondary spray water is 0.5L/min, and the pressure in two-stage spray equipment is all 0.5MPa.
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| CN102532547B true CN102532547B (en) | 2014-02-12 |
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| 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 |
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