CN103450244A - Preparation method of alkyl methyl isoacetoxime silicane - Google Patents
Preparation method of alkyl methyl isoacetoxime silicane Download PDFInfo
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- CN103450244A CN103450244A CN2013103668246A CN201310366824A CN103450244A CN 103450244 A CN103450244 A CN 103450244A CN 2013103668246 A CN2013103668246 A CN 2013103668246A CN 201310366824 A CN201310366824 A CN 201310366824A CN 103450244 A CN103450244 A CN 103450244A
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- methyl isopropyl
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Abstract
The invention discloses a preparation method of alkyl methyl isoacetoxime silicane. The preparation method comprises the following steps: adding methyl isoacetoxime and 120# solvent oil into a reaction kettle, simultaneously and continuously adding chlorosilane and ammonia gas into the reaction kettle and controlling temperature to be 20-40 DEG C to react, wherein the molar ratio of the chlorosilane to the methyl isoacetoxime to the ammonia is 1:(3-3.3):(3-3.3), and the using amount of the 120# solvent oil is 2-3 times the weight of the chlorosilane; filtering to obtain filtrate and ammonium chloride after the reaction is finished, feeding the filtrate into a first thin-film evaporator to remove the 120# solvent oil, and feeding into a second thin-film evaporator to remove the residual methyl isoacetoxime to obtain a product. The method is simple and practical and is suitable for industrial production; the prepared alkyl methyl isoacetoxime silicane has extremely low physiological toxicity, is suitable for being used as a material in close contact with human beings such as medical materials, foods and articles for daily use, and has the characteristics of lower viscosity, easiness in distillation and extraction and relatively high activity.
Description
Technical field
The present invention relates to silane crosslinker synthetic field, particularly a kind of preparation method of alkyl methyl isopropyl acetone oximino silane.
Background technology
The linking agent of ketoxime removing type RTV silicon rubber has following three kinds in the market:
1, take the alkyl Diacetylmonoxime base silane that Diacetylmonoxime is raw material, this system is wide in variety, is current topmost use kind.But, because Diacetylmonoxime has physiology toxicity, it is in a lot of fields, in the preparation such as medical, food, daily necessities etc. and the material of people's close contact, be restricted.In addition, in European Union, this system is restricted, and when Diacetylmonoxime content is greater than 1% in product, must do dangerous sign.
2, take the alkyl acetoxime base silane that acetoxime is raw material.This system mainly contains methyl tri acetylacetonate oximino silane, vinyl tri acetylacetonate oximino silane.But, because acetoxime is a kind of crystal, it only just can dissolve in the virose solvents such as toluene.Therefore, with acetoxime, prepare the acetoxime base silane, operational difficulty, yield is low.And wherein often contain the toxic solvent that is difficult on a small quantity deviate from.Therefore, this system product is difficult to apply.
3, take the alkyl methyl isobutyl ketone oximino silane that methyl isobutyl ketoxime is raw material.This system has very low physiology toxicity, and preparation manipulation is relatively convenient.Shortcoming is that the product viscosity is larger, and distilation is more difficult.Activity is lower, and preparation RTV silicon rubber surface drying is slower.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect that prior art exists, a kind of preparation method of alkyl methyl isopropyl acetone oximino silane is provided, method is simple, be applicable to suitability for industrialized production, the alkyl methyl isopropyl acetone oximino silane of preparation, have low-down physiology toxicity, the material that is applicable to medical, food, daily necessities etc. and people's close contact, viscosity is lower, and distilation is simple, and activity is relatively high.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of preparation method of alkyl methyl isopropyl acetone oximino silane, methyl isopropyl ketoxime and 120# solvent oil are fed in reactor, then by chlorosilane and ammonia, put into continuously in reactor simultaneously, controlling temperature is reacted at 20-40 ℃, chlorosilane: methyl isopropyl ketoxime: the mol ratio of ammonia is 1:(3-3.3): (3-3.3), the 2-3 that the consumption of 120# solvent oil is chlorosilane weight is doubly; After completion of the reaction, product is transported in whizzer and is filtered, obtain filtrate and ammonium chloride, filtrate enters the first film vaporizer, at temperature 80-100 ℃, vacuum tightness-0.07Mpa ~-distilled under 0.09Mpa, deviate from the 120# solvent oil, then enter the second thin-film evaporator, at temperature 100-120 ℃, vacuum tightness-0.09Mpa ~-distilled under 0.098Mpa, deviate from residual methyl isopropyl ketoxime, obtain product.
Raw material of the present invention is methyl isopropyl ketoxime and chlorosilane.Chlorosilane can be METHYL TRICHLORO SILANE, vinyl trichloro silane, phenyl-trichloro-silicane, silicon tetrachloride.Obtain multiple alkyl methyl isopropyl acetone oximino silane: METHYL TRICHLORO SILANE is reacted with the methyl isopropyl ketoxime and is obtained methyl trimethoxy base isopropyl acetone oximino silane; Vinyl trichloro silane reacts with the methyl isopropyl ketoxime and obtains vinyl trimethylammonium isopropyl acetone oximino silane; Phenyl-trichloro-silicane obtains phenyl trimethylammonium isopropyl acetone oximino silane with reacting with the methyl isopropyl ketoxime; Silicon tetrachloride reacts with the methyl isopropyl ketoxime and obtains tetramethyl-isopropyl acetone oximino silane), can select to mix according to the needed surface drying time of RTV silicon rubber, cohesive strength etc. and use.
As preferably, described chlorosilane is a kind of in METHYL TRICHLORO SILANE, vinyl trichloro silane, phenyl-trichloro-silicane, silicon tetrachloride.
As preferably, below described methyl isopropyl ketoxime moisture 200ppm, purity is more than 99%.
Control below methyl isopropyl ketoxime moisture 200ppm, purity is more than 99%, and the product purity of preparation is high like this, and methyl isopropyl ketoxime moisture is during higher than 200ppm, and the purity for preparing alkyl methyl isopropyl acetone oximino silane acquisition product as raw material is low.
As preferably, the preparation method of described methyl isopropyl ketoxime is: take methyl isopropyl Ketone as raw material, with titanium-silicon molecular sieve catalyst catalysis, at 60-90 ℃, react 3-5 hour with ammoniacal liquor and hydrogen peroxide, the mol ratio of methyl isopropyl Ketone and hydrogen peroxide and ammonia is 1:(1-2): (1-4), obtain the methyl isopropyl ketoxime.The methyl isopropyl ketoxime made by present method is a kind of liquid, and while as raw material, preparing alkyl methyl isopropyl acetone oximino silane, result of use is good, and the product purity of acquisition is high, and product performance are good.
As preferably, the titanium-silicon molecular sieve catalyst consumption is every mole of methyl isopropyl Ketone 3-20g.
As preferably, ammonium chloride enters pulverizer and is pulverized, and then enters the boiled bed drying machine, dry after packing.As fertilizer sources, increase economic efficiency.
The invention has the beneficial effects as follows:
1, raw material methyl isopropyl ketoxime is a kind of liquid, is soluble in the sherwood oil equal solvent, so production operation is simple, is applicable to suitability for industrialized production.
2, there is low-down physiology toxicity, be applicable to the material of medical, food, daily necessities etc. and people's close contact.
3, with methyl isobutyl ketoxime base silane system, compare, its viscosity is lower, and distilation is simple, and activity is relatively high.
4, take transparent type RTV silicon rubber prepared as raw material by alkyl methyl isopropyl acetone oximino silane, and take alkyl Diacetylmonoxime base silane under the same terms and compare as transparent type RTV silicon rubber prepared by raw material, it has the higher transparency.
The accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
In figure: 1, reactor, 2, whizzer, 3, pulverizer, 4, the boiled bed drying machine, 5, the first film vaporizer, the 6, second thin-film evaporator.
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.
Embodiment 1:
As shown in Figure 1, methyl isopropyl ketoxime 890kg, 120# solvent oil 800kg, put into that 3000L band stirs and cooling reactor 1 in, then according to METHYL TRICHLORO SILANE: the ratio that the mol ratio of ammonia is 1:3, add continuously METHYL TRICHLORO SILANE and ammonia, METHYL TRICHLORO SILANE rate of addition 100kg/hr, METHYL TRICHLORO SILANE dripping quantity 400kg stops.Control 20 ℃ of temperature of reaction.After having reacted, product is transported in whizzer 2 and is filtered, obtain filtrate and ammonium chloride, ammonium chloride enters pulverizer 3 and is pulverized, and then enters boiled bed drying machine 4, dry rear packing; Filtrate enters the first film vaporizer 5,80 ℃ of temperature, under vacuum tightness-0.07Mpa, distilled, deviate from the 120# solvent oil, then enter the second thin-film evaporator 6,100 ℃ of temperature, under vacuum tightness-0.09Mpa, distilled, deviate from residual methyl isopropyl ketoxime, obtain product 890.4kg(methyl trimethoxy base isopropyl acetone oximino silane), yield 97%.Analysed preparation purity 98.3%(GC), colourity 5(platinum-cobalt colorimetric), chloride ion content is less than the 1ppm(potentiometric titration).
The preparation method of described methyl isopropyl ketoxime is: take methyl isopropyl Ketone as raw material, with titanium-silicon molecular sieve catalyst (commercially available) catalysis, the titanium-silicon molecular sieve catalyst consumption is every mole of methyl isopropyl Ketone 20g, at 60 ℃, with ammoniacal liquor (concentration 30%) and hydrogen peroxide (concentration 30%), react 5 hours, the mol ratio of methyl isopropyl Ketone and hydrogen peroxide and ammonia is 1:1:1, obtains the methyl isopropyl ketoxime.
Embodiment 2:
As shown in Figure 1, methyl isopropyl ketoxime 825kg, 120# solvent oil 800kg, put into that 3000L band stirs and cooling reactor 1 in, then according to vinyl trichloro silane: the ratio that the mol ratio of ammonia is 1:3.3, add continuously vinyl trichloro silane and ammonia, vinyl trichloro silane rate of addition 100kg/hr, vinyl trichloro silane dripping quantity 400kg stops.Control 30 ℃ of temperature of reaction.After having reacted, product is transported in whizzer 2 and is filtered, obtain filtrate and ammonium chloride, ammonium chloride enters pulverizer 3 and is pulverized, and then enters boiled bed drying machine 4, dry rear packing; Filtrate enters the first film vaporizer 5,100 ℃ of temperature, under vacuum tightness-0.09Mpa, distilled, deviate from the 120# solvent oil, then enter the second thin-film evaporator 6,110 ℃ of temperature, under vacuum tightness-0.09Mpa, distilled, deviate from residual methyl isopropyl ketoxime, obtain product 838.6kg(vinyl trimethylammonium isopropyl acetone oximino silane), yield 95.4%.Analysed preparation purity 98.1%(GC), colourity 10(platinum-cobalt colorimetric), chloride ion content is less than the 1ppm(potentiometric titration).
The preparation method of described methyl isopropyl ketoxime is: take methyl isopropyl Ketone as raw material, with titanium-silicon molecular sieve catalyst catalysis, the titanium-silicon molecular sieve catalyst consumption is every mole of methyl isopropyl Ketone 3g, at 90 ℃, with ammoniacal liquor (concentration 25%) and hydrogen peroxide (concentration 30%), react 3 hours, the mol ratio of methyl isopropyl Ketone and hydrogen peroxide and ammonia is 1:2:4, obtains the methyl isopropyl ketoxime.
Embodiment 3:
As shown in Figure 1, methyl isopropyl ketoxime 970kg, 120# solvent oil 1200kg, put into that 3000L band stirs and cooling reactor 1 in, then according to METHYL TRICHLORO SILANE: the ratio that the mol ratio of ammonia is 1:3.1, add continuously METHYL TRICHLORO SILANE and ammonia, METHYL TRICHLORO SILANE rate of addition 100kg/hr, METHYL TRICHLORO SILANE dripping quantity 400kg stops.Control 40 ℃ of temperature of reaction.After having reacted, product is transported in whizzer 2 and is filtered, obtain filtrate and ammonium chloride, ammonium chloride enters pulverizer 3 and is pulverized, and then enters boiled bed drying machine 4, dry rear packing; Filtrate enters the first film vaporizer 5,90 ℃ of temperature, under vacuum tightness-0.08Mpa, distilled, deviate from the 120# solvent oil, then enter the second thin-film evaporator 6,120 ℃ of temperature, under vacuum tightness-0.098Mpa, distilled, deviate from residual methyl isopropyl ketoxime, obtain product 877.6kg(methyl trimethoxy base isopropyl acetone oximino silane), yield 95.6%.Analysed preparation purity 98.5%(GC), colourity 5(platinum-cobalt colorimetric), chloride ion content is less than the 1ppm(potentiometric titration).
The preparation method of described methyl isopropyl ketoxime is: take methyl isopropyl Ketone as raw material, with titanium-silicon molecular sieve catalyst catalysis, the titanium-silicon molecular sieve catalyst consumption is every mole of methyl isopropyl Ketone 10g, at 80 ℃, with ammoniacal liquor (concentration 30%) and hydrogen peroxide (concentration 30%), react 4 hours, the mol ratio of methyl isopropyl Ketone and hydrogen peroxide and ammonia is 1:1:2, obtains the methyl isopropyl ketoxime.
Product structure general formula of the present invention:
Wherein: R can be CH
3-(methyl), CH
2=CH-(vinyl), C
6h
5-(phenyl); X+y=4;
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 (6)
1. the preparation method of an alkyl methyl isopropyl acetone oximino silane, it is characterized in that: methyl isopropyl ketoxime and 120# solvent oil are fed in reactor, then by chlorosilane and ammonia, put into continuously in reactor simultaneously, controlling temperature is reacted at 20-40 ℃, chlorosilane: methyl isopropyl ketoxime: the mol ratio of ammonia is 1:(3-3.3): (3-3.3), the 2-3 that the consumption of 120# solvent oil is chlorosilane weight is doubly; After completion of the reaction, product is transported in whizzer and is filtered, obtain filtrate and ammonium chloride, filtrate enters the first film vaporizer, at temperature 80-100 ℃, vacuum tightness-0.07Mpa ~-distilled under 0.09Mpa, deviate from the 120# solvent oil, then enter the second thin-film evaporator, at temperature 100-120 ℃, vacuum tightness-0.09Mpa ~-distilled under 0.098Mpa, deviate from residual methyl isopropyl ketoxime, obtain product.
2. preparation method according to claim 1 is characterized in that: described chlorosilane is a kind of in METHYL TRICHLORO SILANE, vinyl trichloro silane, phenyl-trichloro-silicane, silicon tetrachloride.
3. preparation method according to claim 1, it is characterized in that: below described methyl isopropyl ketoxime moisture 200ppm, purity is more than 99%.
4. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: the preparation method of described methyl isopropyl ketoxime is: take methyl isopropyl Ketone as raw material, with titanium-silicon molecular sieve catalyst catalysis, at 60-90 ℃, react 3-5 hour with ammoniacal liquor and hydrogen peroxide, the mol ratio of methyl isopropyl Ketone and hydrogen peroxide and ammonia is 1:(1-2): (1-4), obtain the methyl isopropyl ketoxime.
5. preparation method according to claim 4, it is characterized in that: the titanium-silicon molecular sieve catalyst consumption is every mole of methyl isopropyl Ketone 3-20g.
6. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: ammonium chloride enters pulverizer and is pulverized, and then enters the boiled bed drying machine, dry rear packing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111056970A (en) * | 2019-12-23 | 2020-04-24 | 浙江锦华新材料股份有限公司 | Method for removing residual methyl tributyroximo silane in butanone oxime hydrochloride |
| CN111116411A (en) * | 2019-12-23 | 2020-05-08 | 浙江锦华新材料股份有限公司 | Method for removing residual methyl tributyroximo silane in butanone oxime hydrochloride |
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| CN1706850A (en) * | 2005-04-28 | 2005-12-14 | 陈俊光 | Prepn process of organic silicone oximino silane |
| CN101348498A (en) * | 2008-08-29 | 2009-01-21 | 仙桃市蓝天化工有限责任公司 | Preparation of methyl tributanoximo silane |
| CN102079753A (en) * | 2011-01-26 | 2011-06-01 | 湖北新蓝天新材料股份有限公司 | Preparation method of methyl tris-methylethylketoxime silane |
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2013
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| CN101348498A (en) * | 2008-08-29 | 2009-01-21 | 仙桃市蓝天化工有限责任公司 | Preparation of methyl tributanoximo silane |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111056970A (en) * | 2019-12-23 | 2020-04-24 | 浙江锦华新材料股份有限公司 | Method for removing residual methyl tributyroximo silane in butanone oxime hydrochloride |
| CN111116411A (en) * | 2019-12-23 | 2020-05-08 | 浙江锦华新材料股份有限公司 | Method for removing residual methyl tributyroximo silane in butanone oxime hydrochloride |
| CN111116411B (en) * | 2019-12-23 | 2022-10-18 | 浙江锦华新材料股份有限公司 | Method for removing residual methyl tributyrinoxime silane in butanone oxime hydrochloride |
| CN111056970B (en) * | 2019-12-23 | 2022-10-18 | 浙江锦华新材料股份有限公司 | Method for removing residual methyl tributyroximo silane in butanone oxime hydrochloride |
| 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 |
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Application publication date: 20131218 |