CN111116411B - Method for removing residual methyl tributyrinoxime silane in butanone oxime hydrochloride - Google Patents
Method for removing residual methyl tributyrinoxime silane in butanone oxime hydrochloride Download PDFInfo
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- CN111116411B CN111116411B CN201911336319.0A CN201911336319A CN111116411B CN 111116411 B CN111116411 B CN 111116411B CN 201911336319 A CN201911336319 A CN 201911336319A CN 111116411 B CN111116411 B CN 111116411B
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- butanone oxime
- silane
- oxime hydrochloride
- methyl
- tributyrinoxime silane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/14—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention discloses a method for removing methyl tributyrinoxime silane residual in butanone oxime hydrochloride, wherein a blocking agent and water are added into the butanone oxime hydrochloride containing the methyl tributyrinoxime silane, and the molar ratio of the methyl tributyrinoxime silane to the blocking agent to the water is 1:0.5 to 10:100 to 1000, stirring and reacting for 0.2 to 12 hours at the temperature of between 10 and 100 ℃, cooling to room temperature, and filtering to obtain the butanone oxime hydrochloride aqueous solution without the methyl tributyrinoxime silane. The method has the advantages of simple process, wide application range, high removal rate and good economic benefit.
Description
Technical Field
The invention relates to the field of fine chemical engineering, and particularly relates to a method for removing residual methyl tributyl ketoxime silane in butanone oxime hydrochloride.
Background
Ketoxime silane compounds such as methyl-tributyrinoxime silane are indispensable auxiliaries in the related technical fields of organic silicon, organic polymers, composite materials and the like, are organic silicon products with high technology and high added value, and are generally used as crosslinking agents for room-temperature vulcanized silicone rubber and silicone glass cement (neutral).
At present, methyl trichlorosilane and butanone oxime are used as raw materials to react, and methyl trichlorosilane and butanone oxime are generated at the same time to generate methyl trichlorosilane and byproduct butanone oxime hydrochloride which has the characteristics of high viscosity, strong acidity, easy decomposition and explosion under heating and the like. However, a certain amount of methyl tributyl ketoxime silane tends to remain in the byproduct butanone oxime hydrochloride due to the problem of extraction efficiency, and the methyl tributyl ketoxime silane can be hydrolyzed into silanol compounds when meeting water and then further polymerized into siloxane compounds. In the production process of hydroxylamine hydrochloride, a silanol or siloxane compound is often separated by filtration, but the method has the defect of incomplete separation, and the conditions are as described in patent CN 102590011A: on the one hand, the pipeline or equipment is blocked, and even the cleaning is stopped; on the other hand, insoluble solid particles are entrained in the product, and the quality of the hydroxylamine hydrochloride product is seriously influenced.
Disclosure of Invention
The invention overcomes the defects of the prior art, and provides the method for removing the residual methyl tributyl ketoxime silane in the butanone oxime hydrochloride, which has the advantages of simple process, wide application range, high removal rate and good economic benefit.
In order to solve the technical problems, the invention is realized by the following technical scheme: a method for removing residual methyl tributyrinoxime silane in butanone oxime hydrochloride is characterized in that a blocking agent and water are added into the butanone oxime hydrochloride containing the methyl tributyrinoxime silane, wherein the molar ratio of the methyl tributyrinoxime silane to the blocking agent to the water is 1:0.5 to 10:100 to 1000, stirring and reacting for 0.2 to 12 hours at the temperature of between 10 and 100 ℃, cooling to room temperature, and filtering to obtain the butanone oxime hydrochloride aqueous solution without the methyl tributyrinoxime silane.
In a preferred embodiment of the present invention, the molar ratio of methyl tributyrinoxime silane, blocking agent and water is 1:1 to 5:200 to 800
In a preferred embodiment of the present invention, the reaction temperature is 20 to 80 ℃.
In a preferred embodiment of the present invention, the reaction time is 0.5 to 10 hours.
In a preferred embodiment of the present invention, the rotation speed of the stirring is 100 to 1000rpm.
As a preferred embodiment of the invention, the blocking agent is a mixture of trimethylchlorosilane and dimethyldichlorosilane.
As a preferable embodiment of the invention, the molar ratio of the trimethylchlorosilane to the dimethyldichlorosilane is 0.5-4.5: 1.
in a preferred embodiment of the present invention, the molar content of the methyl tributyrinoxime silane in the butanone oxime hydrochloride is 1.1 to 5%.
In the invention, the methyl tributyl ketoxime silane is firstly hydrolyzed into silanol compounds and then further polymerized into siloxane compounds, and the generated silanol and siloxane compounds have hydrophilicity and adhesiveness, which causes incomplete separation and pipeline blockage. The blocking agents of trimethyl chlorosilane and dimethyl dichlorosilane can be combined with hydroxyl in silanol compounds or siloxane compounds, and generated silane compounds are removed by filtration and separation. The method is suitable for treating the butanone oxime hydrochloride with the methyl tributyrinoxime silane residual quantity of more than 1 percent (mol percent), and is particularly suitable for treating the butanone oxime hydrochloride with the methyl tributyrinoxime silane residual quantity of more than 1.1-5 percent (mol percent).
The reaction principle in the invention is as follows:
in the invention, the molar ratio of the methyl tributylketoxime silane, the blocking agent and the water has an important influence on the removal effect. Too much end-capping agent increases the processing cost, and too little results in poor removal effect; too much water usage increases the amount of wastewater, and too little results in poor removal. Therefore, in the present invention, the molar ratio of methyltributanoxime silane, blocking agent, and water is 1:0.5 to 10:100 to 1000, preferably 1:1 to 5:200 to 800.
The reaction temperature has an important influence on the removal effect of the methyl tributyl ketoxime silane. Too high or too low a temperature leads to poor removal. In the present invention, the stirring temperature is controlled to 10 to 100 ℃ and preferably 20 to 80 ℃.
The reaction time has an important influence on the removal effect of the methyl-tributyrinoxime silane, the treatment time and the cost are increased when the reaction time is too long, and the removal effect is deteriorated when the reaction time is too short. In the present invention, the reaction temperature is controlled to be 0.2 to 12 hours, preferably 0.5 to 10 hours.
Compared with the prior art, the invention has the following advantages:
1. the method for removing the residual methyl tributyrinoxime silane in the by-product butanone oxime hydrochloride has the advantages that the process is simple, the methyl tributyrinoxime silane in the butanone oxime hydrochloride can be removed after blocking and filtering, and the process is obviously simplified.
2. The removal efficiency is high, and the removal rate of the methyl tributyroximo silane is more than 97.5 percent and can reach 98.55 percent at most.
3. The method has good economic benefit, when the treated butanone oxime hydrochloride aqueous solution is used for preparing hydroxylamine hydrochloride with high added value, the problems of pipeline blockage and solid particle contained in a salt-hydroxyl product are avoided, the problems of pipeline and equipment blockage caused by residual silicon methyl tributyl oxime silane in the by-product butanone oxime hydrochloride and insoluble solid particle contained in downstream hydroxylamine hydrochloride are solved, and the economic benefit is remarkable.
4. The method has wide application range, and can be widely applied to solving the separation problem of the ketoxime silane compound remained in the byproduct ketoxime salt in the production process of organic silicon products.
5. The method is green and environment-friendly, and the filter cake obtained by filtering can be recycled, thereby remarkably reducing the discharge of three wastes.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.
The byproduct butanone oxime hydrochloride in the embodiment is from a methyl tributyrinoxime silane production device which adopts methyl trichlorosilane and butanone oxime as raw materials.
Example 1
1mol of butanone oxime hydrochloride with the molar percentage of 1.2 percent of methyl tributyrinoxime silane is added into a 1000ml four-neck flask with a mechanical stirring, water cooling return pipe and dropping funnel, 0.012mol of trimethyl chlorosilane, 0.012mol of dimethyl dichlorosilane and 5mol of water are added, the mixture is stirred for 2 hours at the temperature of 60 ℃ and the rotating speed of 600rpm, a filter cake and a butanone oxime hydrochloride aqueous solution are obtained by filtration, and the removal rate of the methyl tributyrinoxime silane is 98.55 percent by sampling and detecting from the butanone oxime hydrochloride aqueous solution.
Example 2
1mol of butanone oxime hydrochloride with the molar percentage of 3.2 percent of methyl tributyrinoxime silane is added into a 1000ml four-neck flask with a mechanical stirring, water cooling return pipe and dropping funnel, 0.025mol of trimethyl chlorosilane, 0.006mol of dimethyl dichlorosilane and 6mol of water are added, the mixture is stirred for 0.5 hour at 80 ℃ and the rotating speed of 500rpm, a filter cake and a butanone oxime hydrochloride aqueous solution are obtained by filtration, and the removal rate of the methyl tributyrinoxime silane is 98.13 percent by sampling and detecting from the butanone oxime hydrochloride aqueous solution.
Example 3
1mol of butanone oxime hydrochloride with the molar percentage of 4.8 percent of methyl tributyrinoxime silane is added into a 1000ml four-neck flask with a mechanical stirring, water cooling return pipe and dropping funnel, 0.03mol of trimethyl chlorosilane, 0.02mol of dimethyl dichlorosilane and 10mol of water are added, the mixture is stirred for 5 hours at 50 ℃ at the rotating speed of 200rpm, a filter cake and a butanone oxime hydrochloride aqueous solution are obtained by filtering, and the removal rate of the methyl tributyrinoxime silane is 97.53 percent by sampling and detecting the butanone oxime hydrochloride aqueous solution.
Example 4
1mol of butanone oxime hydrochloride with the molar percentage of 2.2 percent of methyl tributyrinoxime silane is added into a 1000ml four-neck flask with a mechanical stirring, water cooling return pipe and dropping funnel, 0.08mol of trimethyl chlorosilane, 0.03mol of dimethyl dichlorosilane and 15mol of water are added, the mixture is stirred for 10 hours at the temperature of 20 ℃ and the rotating speed of 300rpm, a filter cake and a butanone oxime hydrochloride aqueous solution are obtained by filtering, and the removal rate of the methyl tributyrinoxime silane is 97.67 percent by sampling and detecting from the butanone oxime hydrochloride aqueous solution.
Example 5
1mol of butanone oxime hydrochloride with the molar percentage of 1.6 percent of methyl tributyl oxime silane, 0.02mol of trimethylchlorosilane, 0.03mol of dimethyldichlorosilane and 5mol of water are added into a 1000ml four-neck flask with a mechanical stirring, water cooling return pipe and dropping funnel, the mixture is stirred for 4 hours at the rotating speed of 350rpm at the temperature of 60 ℃, a filter cake and a butanone oxime hydrochloride aqueous solution are obtained by filtration, and the removal rate of the methyl tributyl oxime silane is 97.75 percent by sampling and detecting the butanone oxime hydrochloride aqueous solution.
Comparative example 1
1mol of butanone oxime hydrochloride with the molar percentage of methyl tributanone oxime silane of 1.2 percent is added into a 1000ml four-neck flask with a mechanical stirring, water cooling reflux pipe and dropping funnel, 5mol of water is added, stirring is carried out for 2 hours at the rotating speed of 600rpm at 60 ℃, a filter cake and a butanone oxime hydrochloride aqueous solution are obtained by filtration, and the removal rate of the methyl tributanone oxime silane is 54.96 percent by sampling and detecting the butanone oxime hydrochloride aqueous solution.
Claims (7)
1. The method for removing the residual methyl tributyrinoxime silane in the butanone oxime hydrochloride is characterized in that a blocking agent and water are added into the butanone oxime hydrochloride containing the methyl tributyrinoxime silane, wherein the molar ratio of the methyl tributyrinoxime silane to the blocking agent to the water is 1:0.5 to 10: and (3) reacting at 10 to 100 ℃ for 0.2 to 12 hours under stirring, cooling to room temperature, and filtering to obtain the butanone oxime hydrochloride aqueous solution with the methyl tributyl ketoxime silane removed, wherein the end-capping agent is a mixture of trimethylchlorosilane and dimethyldichlorosilane.
2. The method for removing the methyl tributyrinoxime silane remained in the butanone oxime hydrochloride as claimed in claim 1, wherein the molar ratio of the methyl tributyrinoxime silane to the blocking agent to the water is 1:1 to 5:200 to 800
3. The method for removing the residual methyltributanoxime silane from butanone oxime hydrochloride according to claim 1, characterized in that the reaction temperature is 20 to 80 ℃.
4. The method for removing the residual methyl tributanone oxime silane in the butanone oxime hydrochloride according to claim 1, wherein the reaction time is 0.5 to 10 hours.
5. The method for removing the residual methyltributanoxime silane from butanone oxime hydrochloride according to claim 1, characterized in that the rotation speed of the stirring is 100 to 1000rpm.
6. The method for removing the residual methyltributanoxime silane from butanone oxime hydrochloride according to claim 1, characterized in that the molar ratio of trimethylchlorosilane to dimethyldichlorosilane is 0.5 to 4.5:1.
7. the method for removing the residual methyl tributyrinoxime silane in the butanone oxime hydrochloride according to claim 1, wherein the molar content of the methyl tributyrinoxime silane in the butanone oxime hydrochloride is 1.1-5%.
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| CN105776160A (en) * | 2016-03-25 | 2016-07-20 | 巨化集团技术中心 | Preparation method of hydroxylammonium chloride |
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| US5359108A (en) * | 1992-09-17 | 1994-10-25 | Alliedsignal Inc. | Di-, tri- and tetrafunctional methyl isobutyl and methyl amyl ketoxime-based silanes |
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