CN103467508A - Preparation method of methyl ketone oxime methoxy silane - Google Patents
Preparation method of methyl ketone oxime methoxy silane Download PDFInfo
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- CN103467508A CN103467508A CN2013103668265A CN201310366826A CN103467508A CN 103467508 A CN103467508 A CN 103467508A CN 2013103668265 A CN2013103668265 A CN 2013103668265A CN 201310366826 A CN201310366826 A CN 201310366826A CN 103467508 A CN103467508 A CN 103467508A
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Abstract
The invention discloses a preparation method of methyl ketone oxime methoxy silane. The method comprises the following steps: (1), adding butanone oxime, methanol and miscella No. 120 into a reaction kettle with a stirring function, then dripping methyl trichlorosilane into the reaction kettle, adjusting dripping speed of the methyl trichlorosilane, and controlling the reaction temperature between 30 DEG C and 60 DEG C; (2), after the dripping is completed, performing still standing for layering, adding an upper-layer product into a first neutralization kettle, pumping ammonia gas for neutralization, then filtering, separating ammonium chloride, and distilling out miscella to obtain a product; adding a lower-layer product into a second neutralization kettle, adding the miscella, pumping ammonia gas for neutralization, then filtering, separating ammonium chloride, and distilling out the No. 120 miscella to obtain the butanone oxime. The method provided by the invention is simple, feasible, suitable for industrial production, high in product yield and low in manufacturing cost; the prepared product has excellent activation, can be used for preparing RTV silicone rubber which meets fast surface dry requirements, and has low possibility of discoloration during storage.
Description
Technical field
The present invention relates to silane crosslinker synthetic field, particularly a kind of preparation method of methyl ketone oximido methoxy silane.
Background technology
The traditional linking agent of the preparation of room curing silicon rubber adopts methyl tributanoximo silane, vinyl tributyl ketoximyl silane.Methyl tributanoximo silane, active low, the RTV silicon rubber of preparation, exist surface drying slow, the shortcomings such as easy cracking.Use vinyl tributyl ketoximyl silane can avoid the above-mentioned shortcoming of methyl three butanone base silanes, but its price is high, cause cost to rise, and vinyl tributyl ketoximyl silane very easy flavescence look in storage process, can be influential when the transparent RTV silicon rubber of preparation.
The disclosure of the invention of CN 102093721 A a kind of linking agent of room temperature vulcanized silicone rubber, described linking agent is the Diacetylmonoxime methoxylsilane, linking agent is methyltrimethoxy silane and 2-butanone oxime, and under the condition of catalyst-free, in the temperature range of 100～150 ℃, reaction 20h left and right makes.This patent does not provide the technology enlightenment that how to prepare methyl ketone oximido methoxy silane.In addition, adopt methyltrimethoxy silane to react preparation methyl ketone oximido methoxy silane with the 2-butanone oxime, respond slow, by-product carbinol is difficult, and transformation efficiency is not high, obtains the shortcomings such as product colourity height.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of methyl ketone oximido methoxy silane, method is simple, be applicable to suitability for industrialized production, product yield is high, and production cost is low, and product has good activity, the RTV silicon rubber that can require for the preparation of fast surface drying, and being not easy variable color in this product stock process, the RTV silicon rubber prepared with this product, have advantages of that stable storing, agglutinating value(of coal) are good.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of preparation method of methyl ketone oximido methoxy silane, described preparation method's step is as follows:
(1) Diacetylmonoxime, methyl alcohol and No. 120 solvent oils are joined in the reactor of band stirring, then in reactor, drip METHYL TRICHLORO SILANE, regulate the rate of addition of METHYL TRICHLORO SILANE, control temperature of reaction at 30-60 ℃; Control temperature of reaction at 30-60 ℃ of transformation efficiency that more is conducive to the carrying out of reaction and improves product.
(2) after dropwising, stratification, the upper strata product enters in first and still, passes into ammonia and is neutralized, and after pH is greater than 7, stops, then filter, after isolating ammonium chloride, obtain the work in-process of methyl ketone oximido methoxy silane, these work in-process are entered to the first film vaporizer, distill out solvent oil No. 120, obtain methyl ketone oximido methoxy silane product; Lower floor's product enters in second and still, add solvent oil No. 120 with still in second, stirring and evenly mixing, pass into ammonia and neutralized, and after pH is greater than 7, stops, then filter, after isolating ammonium chloride, filtrate enters the second thin-film evaporator, distills out solvent oil No. 120, obtain Diacetylmonoxime, Diacetylmonoxime and No. 120 solvent oil recycles.
The upper strata product is product (methyl ketone oximido methoxy silane) and No. 120 oil miscible solvent compounds, and lower floor's product is the Diacetylmonoxime hydrochloride.Lower floor's product is by adding solvent oil No. 120, and the ammonia neutralization, can reclaim Diacetylmonoxime after distillation, reused.
As preferably, METHYL TRICHLORO SILANE in step (1): Diacetylmonoxime: the mol ratio of methyl alcohol is 1:(5-5.5): 1.As preferably, the 1-2 times of weight that in step (1), the consumption of No. 120 solvent oils is METHYL TRICHLORO SILANE.
As preferably, in step (2) in first and the still temperature be controlled at 70-80 ℃.Here control temperature 70-80 ℃, the temperature high solvent is volatilization and dangerous easily; If it is low to control temperature, need to add the high cooling measure of requirement, waste energy.
As preferably, in step (2) in second and the still temperature be controlled at 70-100 ℃.Here control temperature 70-100 ℃, the temperature high solvent is volatilization and dangerous easily; If it is low to control temperature, need to add the high cooling measure of requirement, waste energy.
As preferably, in step (2) in second and the consumption of No. 120 solvent oils that add in the still 2-3 times of weight that is step (1) METHYL TRICHLORO SILANE.
As preferably, the first film evaporator temperature is controlled at 100-120 ℃, vacuum degree control-more than 0.098Mpa.
As preferably, the second thin film evaporation actuator temperature is controlled at 80-90 ℃, vacuum degree control-more than 0.09Mpa.
The invention has the beneficial effects as follows:
1, method is simple, is applicable to suitability for industrialized production, and product yield is high, and production cost is low,
2, product has good cost advantage (lower than methyl three butanone base silane costs), has good activity, and its activity approaches vinyl tributanoximo silicon, the RTV silicon rubber that can require for the preparation of fast surface drying.
3, be not easy variable color in the product stock process.
4, the RTV silicon rubber prepared with product of the present invention, have advantages of that stable storing, agglutinating value(of coal) are good.
The accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below by specific embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, the raw material adopted and equipment etc. all can be buied from market or this area is commonly used.Method in following embodiment, if no special instructions, be the ordinary method of this area.
A kind of preparation method of methyl ketone oximido methoxy silane, as shown in Figure 1, preparation method's step is as follows in technical process:
(1) Diacetylmonoxime, methyl alcohol and No. 120 solvent oils are joined in the reactor of band stirring, then in reactor, drip METHYL TRICHLORO SILANE, regulate the rate of addition of METHYL TRICHLORO SILANE, control temperature of reaction at 30-60 ℃; METHYL TRICHLORO SILANE: Diacetylmonoxime: the mol ratio of methyl alcohol is 1:(5-5.5): the 1-2 that the consumption of 1, No. 120 solvent oil is METHYL TRICHLORO SILANE times weight.
(2) after dropwising, stratification, the upper strata product enters in first and still, passes into ammonia and is neutralized (during in first and still temperature be controlled at 70-80 ℃), after being greater than 7, pH stops, then filter, after isolating ammonium chloride, obtain the work in-process of methyl ketone oximido methoxy silane, these work in-process are entered to the first film vaporizer, distill out No. 120 solvent oils (temperature is controlled at 100-120 ℃, vacuum degree control-more than 0.098Mpa), obtain methyl ketone oximido methoxy silane product; Lower floor's product enters in second and still, add No. 120 solvent oils (2-3 that consumption is METHYL TRICHLORO SILANE times weight) with still in second, stirring and evenly mixing, pass into ammonia and neutralized (during in second and still temperature be controlled at 70-100 ℃), after being greater than 7, pH stops, then filter, after isolating ammonium chloride, filtrate enters the second thin-film evaporator, (temperature is controlled at 80-90 ℃ to distill out No. 120 solvent oils, vacuum degree control-more than 0.09Mpa), obtain Diacetylmonoxime, Diacetylmonoxime and No. 120 solvent oil recycles.
Specific embodiment
Embodiment 1:
At the band of 3000L, stir, in the reactor with circulating water, drop into 1168kg Diacetylmonoxime, 85.6kg methyl alcohol, 400kg120# solvent oil, in the situation that stir, drip METHYL TRICHLORO SILANE 400kg, regulate rate of addition, control 30 ℃ of temperature of reaction, after being added dropwise to complete, keep 30 ℃ of temperature, continue reaction 2 hours.Then standing, layering.Upper strata is product and oil miscible solvent compound, enter in first and still, passing into ammonia is neutralized, 70 ℃ of neutral temperatures stop after pH is greater than 7, then filter, after isolating ammonium chloride, enter the first film vaporizer, distilling off solvent under 100 ℃, the condition of vacuum tightness-0.098Mpa, obtain methyl ketone oximido methoxy silane product.Lower floor is the Diacetylmonoxime hydrochloride, enter in second and still, add the 120# solvent oil of 800kg, pass into ammonia and neutralized, 90 ℃ of neutral temperatures, after being greater than 7, pH stops, then filter, after isolating ammonium chloride, enter the second thin-film evaporator, 80 ℃ ,-the 0.09Mpa vacuum degree condition under distilling off solvent oil, obtain Diacetylmonoxime.Diacetylmonoxime and solvent oil return to use.Statistics obtains product 645kg, and yield 97.9%(calculates by METHYL TRICHLORO SILANE).Methyl ketone oximido methoxy silane content 98.1% in analysed preparation, colourity 10(platinum-cobalt colorimetry), chloride ion content is less than the 1ppm(potentiometric titration).
Embodiment 2:
At the band of 3000L, stir, in the reactor with circulating water, drop into 1238kg Diacetylmonoxime, 85.6kg methyl alcohol, 400kg120# solvent oil, in the situation that stir, drip METHYL TRICHLORO SILANE 400kg, regulate rate of addition, control 40 ℃ of temperature of reaction, after being added dropwise to complete, keep 40 ℃ of temperature, continue reaction 2 hours.Then standing, layering.Upper strata is product and oil miscible solvent compound, enter in first and still, passing into ammonia is neutralized, 75 ℃ of neutral temperatures stop after pH is greater than 7, then filter, after isolating ammonium chloride, enter the first film vaporizer, distilling off solvent under 110 ℃, the condition of vacuum tightness-0.098Mpa, obtain methyl ketone oximido methoxy silane product.Lower floor is the Diacetylmonoxime hydrochloride, enter in second and still, add the 120# solvent oil of 800kg, pass into ammonia and neutralized, 70 ℃ of neutral temperatures, after being greater than 7, pH stops, then filter, after isolating ammonium chloride, enter the second thin-film evaporator, 90 ℃ ,-the 0.09Mpa vacuum degree condition under distilling off solvent oil, obtain Diacetylmonoxime.Diacetylmonoxime and solvent oil return to use.Statistics obtains product 638kg, and yield 96.9%(calculates by METHYL TRICHLORO SILANE).Methyl ketone oximido methoxy silane content 98.0% in analysed preparation, colourity 5(platinum-cobalt colorimetry), chloride ion content is less than the 1ppm(potentiometric titration).
Embodiment 3:
At the band of 3000L, stir, in the reactor with circulating water, drop into 1284kg Diacetylmonoxime, 85.6kg methyl alcohol, 800kg120# solvent oil, in the situation that stir, drip METHYL TRICHLORO SILANE 400kg, regulate rate of addition, control 60 ℃ of temperature of reaction, after being added dropwise to complete, keep temperature 60 C, continue reaction 2 hours.Then standing, layering.Upper strata is product and oil miscible solvent compound, enter in first and still, passing into ammonia is neutralized, 80 ℃ of neutral temperatures stop after pH is greater than 7, then filter, after isolating ammonium chloride, enter the first film vaporizer, distilling off solvent under 120 ℃, the condition of vacuum tightness-0.098Mpa, obtain methyl ketone oximido methoxy silane product.Lower floor is the Diacetylmonoxime hydrochloride, enter in second and still, add the 120# solvent oil of 800kg, pass into ammonia and neutralized, 100 ℃ of neutral temperatures, after being greater than 7, pH stops, then filter, after isolating ammonium chloride, enter the second thin-film evaporator, 90 ℃ ,-the 0.09Mpa vacuum degree condition under distilling off solvent oil, obtain Diacetylmonoxime.Diacetylmonoxime and solvent oil return to use.Statistics obtains product 648kg, and yield 98.4%(calculates by METHYL TRICHLORO SILANE).Methyl ketone oximido methoxy silane content 98.5% in analysed preparation, colourity 10(platinum-cobalt colorimetry), chloride ion content is less than the 1ppm(potentiometric titration).
Product methyl ketone oximido methoxy silane of the present invention is a mixture, and its general formula is:
When x is that 3, y is 0 o'clock, be methyl tributanoximo silane, it is the by product of the present invention's reaction, content is seldom.
Product compositions content of the present invention is as follows:
Methyl tributanoximo silane: 0-5%;
Methyl methoxy base two Diacetylmonoxime base silane: 70-85%;
Methyl dimethoxy oxygen base one Diacetylmonoxime silane: 10-25%.
In product building-up process of the present invention, reaction formula is as follows:
。
Above-described embodiment is a kind of preferably scheme of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim puts down in writing.
Claims (8)
1. the preparation method of a methyl ketone oximido methoxy silane, it is characterized in that: described preparation method's step is as follows:
(1) Diacetylmonoxime, methyl alcohol and No. 120 solvent oils are joined in the reactor of band stirring, then in reactor, drip METHYL TRICHLORO SILANE, regulate the rate of addition of METHYL TRICHLORO SILANE, control temperature of reaction at 30-60 ℃;
(2) after dropwising, stratification, the upper strata product enters in first and still, passes into ammonia and is neutralized, and after pH is greater than 7, stops, then filter, after isolating ammonium chloride, obtain the work in-process of methyl ketone oximido methoxy silane, these work in-process are entered to the first film vaporizer, distill out solvent oil No. 120, obtain methyl ketone oximido methoxy silane product; Lower floor's product enters in second and still, add solvent oil No. 120 with still in second, stirring and evenly mixing, pass into ammonia and neutralized, and after pH is greater than 7, stops, then filter, after isolating ammonium chloride, filtrate enters the second thin-film evaporator, distills out solvent oil No. 120, obtain Diacetylmonoxime, Diacetylmonoxime and No. 120 solvent oil recycles.
2. preparation method according to claim 1 is characterized in that: METHYL TRICHLORO SILANE in step (1): Diacetylmonoxime: the mol ratio of methyl alcohol is 1:(5-5.5): 1.
3. preparation method according to claim 2, is characterized in that: the 1-2 times of weight that in step (1), the consumption of No. 120 solvent oils is METHYL TRICHLORO SILANE.
4. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: in step (2) in first and the still temperature be controlled at 70-80 ℃.
5. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: in step (2) in second and the still temperature be controlled at 70-100 ℃.
6. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: in step (2) in second and the consumption of No. 120 solvent oils that add in the still 2-3 times of weight that is step (1) METHYL TRICHLORO SILANE.
7. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: the first film evaporator temperature is controlled at 100-120 ℃, vacuum degree control-more than 0.098Mpa.
8. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: the second thin film evaporation actuator temperature is controlled at 80-90 ℃, vacuum degree control-more than 0.09Mpa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109971180A (en) * | 2019-02-25 | 2019-07-05 | 袁玲燕 | A kind of high-temperature resistant heat-conducting silicone grease and preparation method thereof |
| CN111018900A (en) * | 2019-12-25 | 2020-04-17 | 浙江锦华新材料股份有限公司 | Preparation method of methyl tributyl ketoxime silane |
| CN111807989A (en) * | 2020-07-15 | 2020-10-23 | 浙江圣安化工股份有限公司 | Method for treating ketoxime hydrochloride |
| CN112142771A (en) * | 2020-09-29 | 2020-12-29 | 江苏艾科维科技有限公司 | Recovery method of ketoxime type hydrochloride and corresponding production method of ketoxime type silane |
| CN113980476A (en) * | 2021-11-09 | 2022-01-28 | 湖北君健新材料股份有限公司 | Anti-tarnish agent composite composition and application thereof |
| CN114621284A (en) * | 2021-11-26 | 2022-06-14 | 浙江衢州硅宝化工有限公司 | Preparation method of methyl diketone oximido alkoxysilane |
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| CN102093721A (en) * | 2010-09-14 | 2011-06-15 | 抚顺哥俩好化学有限公司 | Single-component alcohol/ketoxime-removed room temperature vulcanizing silicone rubber and preparation method thereof |
| CN102924500A (en) * | 2012-10-26 | 2013-02-13 | 湖北新蓝天新材料股份有限公司 | Preparation method of alkoxymethylethylketoxime silane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093721A (en) * | 2010-09-14 | 2011-06-15 | 抚顺哥俩好化学有限公司 | Single-component alcohol/ketoxime-removed room temperature vulcanizing silicone rubber and preparation method thereof |
| CN102924500A (en) * | 2012-10-26 | 2013-02-13 | 湖北新蓝天新材料股份有限公司 | Preparation method of alkoxymethylethylketoxime silane |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109971180A (en) * | 2019-02-25 | 2019-07-05 | 袁玲燕 | A kind of high-temperature resistant heat-conducting silicone grease and preparation method thereof |
| CN111018900A (en) * | 2019-12-25 | 2020-04-17 | 浙江锦华新材料股份有限公司 | Preparation method of methyl tributyl ketoxime silane |
| CN111807989A (en) * | 2020-07-15 | 2020-10-23 | 浙江圣安化工股份有限公司 | Method for treating ketoxime hydrochloride |
| CN112142771A (en) * | 2020-09-29 | 2020-12-29 | 江苏艾科维科技有限公司 | Recovery method of ketoxime type hydrochloride and corresponding production method of ketoxime type silane |
| CN112142771B (en) * | 2020-09-29 | 2023-05-05 | 江苏艾科维科技有限公司 | Recovery method of ketoxime hydrochloride and corresponding ketoxime silane production method |
| CN113980476A (en) * | 2021-11-09 | 2022-01-28 | 湖北君健新材料股份有限公司 | Anti-tarnish agent composite composition and application thereof |
| CN114621284A (en) * | 2021-11-26 | 2022-06-14 | 浙江衢州硅宝化工有限公司 | Preparation method of methyl diketone oximido alkoxysilane |
| CN114621284B (en) * | 2021-11-26 | 2024-03-01 | 浙江衢州硅宝化工有限公司 | Preparation method of methyldiketone oxime alkoxy silane |
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Denomination of invention: Preparation method of methyl ketone oxime methoxy silane Effective date of registration: 20180103 Granted publication date: 20150930 Pledgee: China Co truction Bank Corp of Quzhou Province Branch Pledgor: Zhejiang Quzhou Guibao Chemical Co., Ltd. Registration number: 2017330000346 |