CN110835355A - Synthesis process of high-purity bis [ (3-trialkoxysilyl) -propyl ] amine - Google Patents
Synthesis process of high-purity bis [ (3-trialkoxysilyl) -propyl ] amine Download PDFInfo
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- CN110835355A CN110835355A CN201810927061.0A CN201810927061A CN110835355A CN 110835355 A CN110835355 A CN 110835355A CN 201810927061 A CN201810927061 A CN 201810927061A CN 110835355 A CN110835355 A CN 110835355A
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- propyl
- trialkoxysilyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
Abstract
The invention discloses a synthesis process of high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, which comprises the following steps: the method comprises the following steps of firstly, taking chloropropyltrialkoxysilane and aminopropyltrialkoxysilane as raw materials, dropwise adding the chloropropyltrialkoxysilane into the aminopropyltrialkoxysilane in an inert gas atmosphere, and preserving heat after dropwise adding; secondly, adding a dechlorinating agent into the system, stirring and carrying out dechlorinating reaction; thirdly, cooling after the dechlorination reaction is finished, and separating the precipitated salt out of the system to obtain a reaction solution; introducing ammonia gas into the reaction liquid, stirring, filtering out insoluble salt after the reaction is finished, and obtaining reaction liquid containing bis [ (3-trialkoxysilyl) -propyl ] amine; fifthly, distilling the reaction liquid containing the bis [ (3-trialkoxysilyl) -propyl ] amine under reduced pressure to obtain a finished product of the bis [ (3-trialkoxysilyl) -propyl ] amine; the invention has the advantages that: the product yield is greatly improved, and the product purity is also greatly improved.
Description
Technical Field
The invention relates to the technical field of synthesis of bis [ (3-trialkoxysilyl) -propyl ] amine.
Background
Bis [ (3-trialkoxysilyl) -propyl ] amine is widely applied to the industries of coating, casting, gluing, curing, electronic packaging and the like. The market situation of the bis [ (3-trialkoxysilyl) -propyl ] amine which is short in supply and short in demand has been continued for many years, and the reason is that the bis [ (3-trialkoxysilyl) -propyl ] amine is mostly obtained by a series of chemical treatment processes from the corresponding rectified high-boiling residue of aminopropyltrialkoxysilane. The amount of bis [ (3-trialkoxysilyl) -propyl ] amine produced by the rectified high boiler process is far from meeting market demands due to the limited yield of rectified high boilers of aminopropyltrialkoxysilanes, and the purity of such bis [ (3-trialkoxysilyl) -propyl ] amine produced by rectified high boilers is usually only 95% for process reasons.
Disclosure of Invention
The purpose of the invention is: provides a synthesis process of high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, which has high yield and high purity.
In order to achieve the purpose, the invention adopts the technical scheme that: the synthesis process of high-purity bis [ (3-trialkoxysilyl) -propyl ] amine comprises the following steps: the method comprises the following steps of firstly, taking chloropropyltrialkoxysilane and aminopropyltrialkoxysilane as raw materials, dropwise adding the chloropropyltrialkoxysilane into the aminopropyltrialkoxysilane in an inert gas atmosphere, and preserving heat after dropwise adding; secondly, adding a dechlorinating agent into the system, stirring and carrying out dechlorinating reaction; thirdly, cooling after the dechlorination reaction is finished, and separating the precipitated salt out of the system to obtain a reaction solution; introducing ammonia gas into the reaction liquid, stirring, filtering out insoluble salt after the reaction is finished, and obtaining reaction liquid containing bis [ (3-trialkoxysilyl) -propyl ] amine; fifthly, distilling the reaction liquid containing the bis [ (3-trialkoxysilyl) -propyl ] amine under reduced pressure to obtain a finished product of the bis [ (3-trialkoxysilyl) -propyl ] amine; the reaction equation in step one is as follows:
in the above reaction equation, R1 represents an alkoxy group.
Further, the aforementioned high purity bis [ (3-trialkoxysilyl) -propyl ] group]Process for the synthesis of amines wherein R1 represents an alkoxy group comprising-OCH3，-OC2H5，-OC3H7，-OC4H9。
Further, in the synthesis process of the high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, in the step one, the reaction temperature of chloropropyltrialkoxysilane and aminopropyltrialkoxysilane is controlled to be 30-70 ℃, the dropping time is controlled to be 1-2 hours, and the heat preservation time is 2-4 hours.
Further, in the synthesis process of the high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, the time for dechlorination in the second step is 1 hour.
Further, in the synthesis process of the high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, in the third step, the temperature is reduced to 20-40 ℃ after the dechlorination reaction is finished.
Further, in the synthesis process of the high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, in the fourth step, the temperature of the introduced ammonia gas is controlled to be 20-40 ℃ during stirring, the time of the introduced ammonia gas is controlled to be 0.5-2 hours during stirring, and after the reaction is finished, insoluble salts are filtered out.
Further, in the synthesis process of the high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, in the fifth step, the pressure of reduced pressure distillation is controlled to be-0.1 MPa.
Further, in the synthesis process of the high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, in the step one, nitrogen is used as inert gas.
Further, in the synthesis process of the high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, the dechlorinating agent is one of sodium methoxide, sodium ethoxide, ethylenediamine, triethylamine, diethylamine, diethylenetriamine and triethylenetetramine.
Furthermore, in the synthesis process of the high-purity bis [ (3-trialkoxysilyl) -propyl ] amine, the dosage of the dechlorinating agent is increased by 10-40% based on a theoretical calculated value.
The invention has the advantages that: firstly, chloropropyl trialkoxysilane and aminopropyl trialkoxysilane are taken as raw materials to be directly combined into bis [ (3-trimethoxy silicon-based) -propyl ] amine, so that the yield of the bis [ (3-trimethoxy silicon-based) -propyl ] amine is greatly improved. Chlorine removal is carried out by adding a chlorine removal agent in the second step and ammonia gas in the fourth step, so that the final content of total chlorine is less than 20ppm, decomposition impurities during rectification are effectively reduced, and the product purity is greatly improved.
Detailed Description
The synthesis of high purity bis [ (3-trialkoxysilyl) -propyl ] amine is described in further detail below.
The synthesis process of high purity bis [ (3-trialkoxysilyl) -propyl ] amine includes the following steps.
The method comprises the steps of taking chloropropyltrialkoxysilane and aminopropyltrialkoxysilane as raw materials, and dropwise adding the chloropropyltrialkoxysilane into the aminopropyltrialkoxysilane in an inert gas atmosphere, wherein the commonly used inert gas is nitrogen. And (3) after dropwise adding is finished for 1-2 hours, keeping the temperature, controlling the reaction temperature to be 30-70 ℃, and keeping the temperature for 2-4 hours.
The reaction equation is as follows:
in the above reaction equation, R1 represents an alkoxy group. Specifically, alkoxy groups include-OCH3，-OC2H5，-OC3H7，-OC4H9。
And secondly, adding a dechlorinating agent into the system, stirring and carrying out dechlorinating reaction. The dechlorinating agent is one of sodium methoxide, sodium ethoxide, ethylenediamine, triethylamine, diethylamine, diethylenetriamine and triethylene tetramine. The dosage of the dechlorinating agent is increased by 10 to 40 percent on the basis of a theoretical calculated value. The theoretical calculation is the amount required for complete reaction. The time for the dechlorination reaction was 1 hour.
And thirdly, cooling to 20-40 ℃ after the dechlorination reaction is finished, and separating out the precipitated salt to obtain a reaction solution.
And fourthly, introducing ammonia gas into the reaction liquid, stirring, controlling the stirring time to be 0.5-2 hours, controlling the temperature to be 20-40 ℃, filtering out insoluble salt after the reaction is finished, and obtaining the reaction liquid containing the bis [ (3-trialkoxysilyl) -propyl ] amine, wherein the total chlorine content in the reaction liquid containing the bis [ (3-trialkoxysilyl) -propyl ] amine is less than 20 ppm. The total chlorine is controlled below 20ppm, so that the decomposed impurities generated by rectification are reduced, and the product purity can be effectively improved.
And fifthly, carrying out reduced pressure distillation on the reaction liquid containing the bis [ (3-trialkoxysilyl) -propyl ] amine, and controlling the pressure to be-0.1 MPa to obtain the finished product of the bis [ (3-trialkoxysilyl) -propyl ] amine. The purity of the finished product is more than 98 percent.
The present invention will be described in further detail with reference to the following examples.
Example 1.
Firstly, adding 1100g of aminopropyltrimethoxysilane into a 2L three-neck flask in a nitrogen atmosphere, heating to 60 ℃, dropwise adding 413g of chloropropyltrimethoxysilane for 2 hours, keeping the temperature for reaction for 3 hours after dropwise adding, taking a reaction liquid sample, detecting that the chlorine content is 46213ppm and is close to a theoretical value, and indicating that the reaction is complete. Secondly, adding 257g of diethylenetriamine into the reaction system, and stirring for l hours at 60 ℃ to carry out dechlorination reaction. And thirdly, after the dechlorination reaction is finished, cooling to 30 ℃, separating the precipitated diethylenetriamine hydrochloride to obtain 1326g of filtrate, and detecting to obtain 198.65ppm of chlorine content in the filtrate. And fourthly, introducing ammonia gas into the filtrate for bubbling for 1 hour, controlling the temperature at 40 ℃, filtering to remove ammonium chloride salt to obtain reaction liquid of the bis [ (3-trimethoxysilyl) -propyl ] amine, weighing 1278g totally, and detecting the total chlorine content of 17.23 ppm. And fifthly, distilling the reaction liquid of the bis [ (3-trimethoxysilyl) -propyl ] amine under reduced pressure, controlling the pressure to be-0.1 MPa, extracting a finished product of the bis [ (3-trimethoxysilyl) -propyl ] amine when the temperature of the kettle is 182 ℃, and stopping distillation until the temperature of the kettle is 205 ℃. 461g of finished product of bis [ (3-trimethoxysilyl) -propyl ] amine is obtained, the detected purity is 98.65 percent, and the chlorine content is 10.22 ppm.
Example 2.
Firstly, adding 1193g of aminopropyltriethoxysilane into a 2L three-neck flask under the nitrogen atmosphere, heating to 70 ℃, dropwise adding 433g of chloropropyltriethoxysilane for 1.5 hours, keeping the temperature for reaction for 4 hours after dropwise adding is finished, taking a reaction liquid sample, detecting that the chlorine content is 38740ppm and is close to a theoretical value, and indicating that the reaction is complete basically. Secondly, adding 142g of ethylenediamine into the reaction system, and stirring at 60 ℃ for 1 hour to perform dechlorination reaction. And thirdly, after the chlorine removal reaction is finished, cooling to 30 ℃, separating out precipitated ethylenediamine hydrochloride, leaving 1476g of filtrate, and detecting to obtain 178.87ppm of chlorine content in the filtrate. And fourthly, introducing ammonia gas into the filtrate, bubbling for 1 hour, controlling the temperature at 20 ℃, filtering to remove ammonium chloride salt to obtain a bis [ (3-triethoxysilyl) -propyl ] amine reaction solution, weighing 1417g totally, and detecting the total chlorine content of 15.88 ppm. And fifthly, distilling the reaction liquid of the bis [ (3-triethoxysilyl) -propyl ] amine under reduced pressure, controlling the pressure to be-0.1 MPa, extracting the finished product of the bis [ (3-triethoxysilyl) -propyl ] amine when the temperature of the kettle is 195 ℃, and stopping distillation until the temperature of the kettle is 215 ℃. 482g of finished product of bis [ (3-triethoxysilyl) -propyl ] amine with the detection purity of 98.36% and the chlorine content of 9.25ppm are obtained.
From the above, the synthesis process of high-purity bis [ (3-trialkoxysilyl) -propyl ] amine according to the present invention has the following advantages: firstly, chloropropyl trialkoxysilane and aminopropyl trialkoxysilane are taken as raw materials to be directly combined into bis [ (3-trimethoxy silicon-based) -propyl ] amine, so that the yield of the bis [ (3-trimethoxy silicon-based) -propyl ] amine is greatly improved. Chlorine removal is carried out by adding a chlorine removal agent in the second step and ammonia gas in the fourth step, so that the final content of total chlorine is less than 20ppm, decomposition impurities during rectification are effectively reduced, and the product purity is greatly improved.
Claims (10)
1. The synthesis process of high-purity bis [ (3-trialkoxysilyl) -propyl ] amine is characterized by comprising the following steps: the method comprises the following steps: the method comprises the following steps of firstly, taking chloropropyltrialkoxysilane and aminopropyltrialkoxysilane as raw materials, dropwise adding the chloropropyltrialkoxysilane into the aminopropyltrialkoxysilane in an inert gas atmosphere, and preserving heat after dropwise adding; secondly, adding a dechlorinating agent into the system, stirring and carrying out dechlorinating reaction; thirdly, cooling after the dechlorination reaction is finished, and separating the precipitated salt out of the system to obtain a reaction solution; introducing ammonia gas into the reaction liquid, stirring, filtering out insoluble salt after the reaction is finished, and obtaining reaction liquid containing bis [ (3-trialkoxysilyl) -propyl ] amine; fifthly, distilling the reaction liquid containing the bis [ (3-trialkoxysilyl) -propyl ] amine under reduced pressure to obtain a finished product of the bis [ (3-trialkoxysilyl) -propyl ] amine; the reaction equation in step one is as follows:
in the above reaction equation, R1 represents an alkoxy group.
2. The high purity bis [ (3-trialkoxysilyl) -propyl ] according to claim 1]The synthesis process of amine is characterized by comprising the following steps: r1 represents alkoxy, the alkoxy includes-OCH3，-OC2H5，-OC3H7，-OC4H9。
3. The process for the synthesis of high purity bis [ (3-trialkoxysilyl) -propyl ] amine according to claim 1, wherein: in the first step, the reaction temperature of chloropropyltrialkoxysilane and aminopropyltrialkoxysilane is controlled to be 30-70 ℃, the dropping time is controlled to be 1-2 hours, and the heat preservation time is 2-4 hours.
4. The process for the synthesis of high purity bis [ (3-trialkoxysilyl) -propyl ] amine according to claim 1, wherein: in the second step, the time of dechlorination reaction is 1 hour.
5. The process for the synthesis of high purity bis [ (3-trialkoxysilyl) -propyl ] amine according to claim 1, wherein: in the third step, the temperature is reduced to 20-40 ℃ after the dechlorination reaction is finished.
6. The process for the synthesis of high purity bis [ (3-trialkoxysilyl) -propyl ] amine according to claim 1, wherein: and in the fourth step, the temperature is controlled to be 20-40 ℃ when ammonia gas is introduced and stirred, the time for introducing ammonia gas and stirring is controlled to be 0.5-2 hours, and insoluble salt is filtered out after the reaction is finished.
7. The process for the synthesis of high purity bis [ (3-trialkoxysilyl) -propyl ] amine according to claim 1, wherein: in the fifth step, the pressure of the reduced pressure distillation is controlled at-0.1 MPa.
8. The process for the synthesis of high purity bis [ (3-trialkoxysilyl) -propyl ] amine according to claim 1, 2, 3, 4, 5, 6 or 7, characterized in that: in the first step, nitrogen is used as the inert gas.
9. The process for the synthesis of high purity bis [ (3-trialkoxysilyl) -propyl ] amine according to claim 1, 2, 3, 4, 5, 6 or 7, characterized in that: the dechlorinating agent is one of sodium methoxide, sodium ethoxide, ethylenediamine, triethylamine, diethylamine, diethylenetriamine and triethylene tetramine.
10. The process for the synthesis of high purity bis [ (3-trialkoxysilyl) -propyl ] amine according to claim 9, wherein: the dosage of the dechlorinating agent is increased by 10 to 40 percent on the basis of a theoretical calculated value.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075235A (en) * | 2020-08-13 | 2022-02-22 | 张家港市国泰华荣化工新材料有限公司 | Continuous production process of bis [ (3-trimethoxysilyl) -propyl ] amine |
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| CN104086584A (en) * | 2014-07-29 | 2014-10-08 | 荆州市江汉精细化工有限公司 | Preparation method of bis-(alkoxysilylpropyl)-amine |
| DE102015225879A1 (en) * | 2015-12-18 | 2017-06-22 | Evonik Degussa Gmbh | Tris- (alkylalkoxysilyl) amine-rich compositions, their preparation and their use |
| CN107778325A (en) * | 2016-08-29 | 2018-03-09 | 张家港市国泰华荣化工新材料有限公司 | The preparation method of N [3 (trimethoxy silicon substrate) propyl group] n-butylamine |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102300869A (en) * | 2009-01-30 | 2011-12-28 | 瓦克化学股份公司 | Process for preparing bis- and tris(silylorgano)amines |
| JP2011162500A (en) * | 2010-02-12 | 2011-08-25 | Shin-Etsu Chemical Co Ltd | Method for producing cyclic silazane compound |
| CN104086584A (en) * | 2014-07-29 | 2014-10-08 | 荆州市江汉精细化工有限公司 | Preparation method of bis-(alkoxysilylpropyl)-amine |
| DE102015225879A1 (en) * | 2015-12-18 | 2017-06-22 | Evonik Degussa Gmbh | Tris- (alkylalkoxysilyl) amine-rich compositions, their preparation and their use |
| CN107778325A (en) * | 2016-08-29 | 2018-03-09 | 张家港市国泰华荣化工新材料有限公司 | The preparation method of N [3 (trimethoxy silicon substrate) propyl group] n-butylamine |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114075235A (en) * | 2020-08-13 | 2022-02-22 | 张家港市国泰华荣化工新材料有限公司 | Continuous production process of bis [ (3-trimethoxysilyl) -propyl ] amine |
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Application publication date: 20200225 |