CN109824714B - Synthetic method of cyclic silicon nitrogen amino silane - Google Patents
Synthetic method of cyclic silicon nitrogen amino silane Download PDFInfo
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- CN109824714B CN109824714B CN201910165241.4A CN201910165241A CN109824714B CN 109824714 B CN109824714 B CN 109824714B CN 201910165241 A CN201910165241 A CN 201910165241A CN 109824714 B CN109824714 B CN 109824714B
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Abstract
The invention relates to a synthetic method of cyclic silicon nitrogen amino silane, belonging to the technical field of fine chemical engineering. According to the invention, aminosilane is stirred and reacts for 3-4 hours at 65-80 ℃ under the action of metal and alkali double catalysts, and then the cyclic silicon-nitrogen aminosilane product is obtained by distillation. The synthesis method has the advantages of high product yield, high content, simple process equipment, recyclable catalyst, safe and environment-friendly by-product which can be used for other industrial purposes.
Description
Technical Field
The invention relates to a synthetic method of cyclic silicon nitrogen amino silane, belonging to the technical field of fine chemical engineering.
Background
Aminosilane is one of the most widely applied silane coupling agent products, is widely applied to products such as epoxy resin, phenolic resin, polyurethane, polycarbonate, polyethylene, polyvinyl chloride, polyamide and the like, can also be used for synthesizing amino modified silicone oil to be used as a fabric softening finishing agent, a polishing agent, a coating, a cosmetic auxiliary agent, organic resin modification and the like, and is used as a cross-linking agent, a tackifier and the like of room-temperature vulcanized silicone rubber. In the use process of the amino silane, the organic functional group generates reactivity conflict with the active group of the organic material of an application system, such as resin, elastomer and the like, thereby limiting the use range and the use effect of the amino silane. Aminosilane is an excellent adhesion promoter and is widely used in a large field, such as surface treatment of glass fibers, modification of engineering plastics, adhesion promoters of coatings, adhesion promoters of adhesives and sealants, and the like, but in a single-component epoxy resin coating, amino groups and epoxy can react, so that the amino groups cannot be directly added and can only be used as a primer or added in a two-component form, and the use process is complicated and the performance is reduced. Moreover, the alkaline nature of aminosilanes leads to a decrease in the stability and a shorter storage period of certain systems, such as RTV-1 alcohol-type gums, furan resins. In order to solve these problems, the amino functional group of aminosilane is cyclized to form cyclic silazane, and the cyclic silazane is added to these systems, and under the conditions of water, alcohol, and the like, the cyclic silazane opens a ring, and the amino functional group is reproduced, thereby exerting its original effect. However, the prior industrial product of the cyclic silicon-nitrogen aminosilane adopts chloroalkyl dialkoxy chlorosilane and ammonia substances such as liquid ammonia, ethylenediamine, aniline, butylamine and the like to carry out ammoniation reaction under certain conditions, so that the side reaction is more, the number of byproduct ammonia salts is more, the effective content of the cyclic silicon-nitrogen aminosilane is only 30-50%, and the market application and sale of the cyclic silicon-nitrogen aminosilane are limited.
Disclosure of Invention
The invention aims to: the synthesis method of the cyclic silicon-nitrogen aminosilane has the characteristics of high product yield, high content, low energy consumption, simple process equipment, low production cost and the like, and is safe and environment-friendly.
The technical scheme of the invention is as follows:
a synthetic method of cyclic silicon nitrogen amino silane is characterized in that: it comprises the following steps:
1) putting aminosilane into a reaction container, and adding a transition metal catalyst accounting for 0.05-0.1% of the weight of the added aminosilane; then adding 10ppm to 100ppm of alkali catalyst based on the weight of the added aminosilane;
2) after the feeding is finished, heating to 65-80 ℃ at a stirring speed of 120-150 rpm, and then carrying out heat preservation reaction for 3-4 hours to obtain a crude product of the cyclic silicon-nitrogen aminosilane;
3) distilling the crude product of the cyclosilazane aminosilane by a distillation device under the pressure of-0.01 MPa to obtain a product of the cyclosilazane aminosilane;
the aminosilane is aminopropyltriethoxysilane (KH-550) or aminoethyl-aminopropyltrimethoxysilane (KH-792).
The transition metal catalyst is nickel powder or zinc powder.
The alkali catalyst is sodium methoxide or sodium ethoxide.
The structural formula of the synthesized cyclic silicon nitrogen amino silane is as follows:
the invention has the beneficial effects that:
1. the metal catalyst and the alkali catalyst are used in small amount and can be recycled after being filtered.
2. The by-products generated by the synthesis are methanol or ethanol and silane polymers, and the methanol or the ethanol can be used for other industrial purposes, and is safe and environment-friendly.
3. The reaction equipment is simple, and the content and the yield of the cyclic silicon nitrogen aminosilane product are high by adopting a double catalytic condensation process.
4. Two aminosilane raw materials, aminopropyltriethoxysilane (KH-550) and aminoethyl-aminopropyltrimethoxysilane (KH-792), are readily available.
5. And corresponding sodium methoxide or sodium ethoxide base catalyst is added according to the properties of the aminosilane raw material, so that other impurities are avoided being brought, and the purity of the product is ensured.
Detailed description of the preferred embodiments
Example 1
Adding 2.0mol (442.7 g) of aminopropyltriethoxysilane (KH-550) into a 1L three-neck flask, adding 0.3 g of nickel powder and 0.02 g of sodium ethoxide, after the feeding is finished, opening the stirring, wherein the stirring speed is 150 rpm, raising the temperature of the kettle to 75 ℃, keeping the temperature, reacting for 3 hours, taking a crude product solution in the flask, and detecting the content by using a gas chromatograph, wherein the content of the aminopropyltriethoxysilane (KH-550) is 1.35%, the content of the cyclosiloxane aminosilane is 78.16%, and the content of ethanol is 20.49%.
The reaction device is changed into a distillation device, brine with the temperature of 20 ℃ below zero is adopted for condensation, distillation is carried out under the pressure of 0.01MPa below zero, 90.7 g of ethanol and 338.4 g of cyclosilazane are obtained, 13.9 g of materials containing the catalyst are remained in the bottle, and the materials are cooled and filtered to obtain 0.4 g of catalyst and 13.5 g of silane polymer. The ethanol and silane polymer can be used for other industrial purposes, and the catalyst can be recycled.
The content of the cyclic silicon-nitrogen aminosilane detected by gas chromatography is 99.4%, and the molar yield of the cyclic silicon-nitrogen aminosilane product is 96.5%.
Example 2
Adding 2.0mol (442.7 g) of aminopropyltriethoxysilane (KH-550) into a 1L three-neck flask, adding 0.3 g of nickel powder and 0.02 g of sodium ethoxide, after the feeding is finished, opening the stirring, wherein the stirring speed is 150 rpm, raising the temperature of the kettle to 75 ℃, keeping the temperature, reacting for 3 hours, taking a crude product solution in the flask, and detecting the content by using a gas chromatograph, wherein the content of the aminopropyltriethoxysilane (KH-550) is 1.41%, the content of the cyclosiloxane aminosilane is 78.13%, and the content of ethanol is 20.46%.
The reaction device is changed into a distillation device, brine with the temperature of 20 ℃ below zero is adopted for condensation, distillation is carried out under the pressure of 0.01MPa below zero, 90.5 g of ethanol and 338.2 g of cyclosilazane are obtained, 14.3 g of materials containing the catalyst are remained in the bottle, and the materials are cooled and filtered to obtain 0.5 g of catalyst and 13.8 g of silane polymer. The ethanol and silane polymer can be used for other industrial purposes, and the catalyst can be recycled.
The content of the cyclic silicon-nitrogen aminosilane detected by gas chromatography is 99.5%, and the molar yield of the cyclic silicon-nitrogen aminosilane product is 96.4%.
Example 3
2.0mol (442.7 g) of aminopropyltriethoxysilane (KH-550) is added into a 1L three-neck flask, 0.4 g of the catalyst obtained by filtration in example 1 is added, after the feeding is finished, the stirring is started, the stirring speed is 150 r/min, the kettle is heated to 75 ℃ for heat preservation reaction for 3 hours, and then the crude product solution in the flask is taken and used for detecting the content by gas chromatography, wherein the content of the aminopropyltriethoxysilane (KH-550) is 1.38%, the content of the cyclosiloxane aminosilane is 78.15%, and the content of ethanol is 20.47%.
The reaction device is changed into a distillation device, brine with the temperature of 20 ℃ below zero is adopted for condensation, distillation is carried out under the pressure of 0.01MPa below zero, 90.4 g of ethanol and 338.9 g of cyclosilazane are obtained, 13.8 g of materials containing the catalyst are remained in the bottle, and the materials are cooled and filtered to obtain 0.4 g of catalyst and 13.4 g of silane polymer. The ethanol and silane polymer can be used for other industrial purposes, and the catalyst can be recycled.
The content of the cyclic silicon-nitrogen aminosilane detected by gas chromatography is 99.5%, and the molar yield of the cyclic silicon-nitrogen aminosilane product is 96.6%.
Example 4
10.0mol (2213.7 g) of aminopropyltriethoxysilane (KH-550) is added into a 3L three-neck flask, 2.0 g of zinc powder and 0.2 g of sodium ethoxide are added, after the feeding is finished, the stirring is started, the stirring speed is 150 r/min, the kettle is heated to 75 ℃ for heat preservation reaction for 3 hours, and then the crude product solution in the flask is taken and used for detecting the content by gas chromatography, wherein the content of the aminopropyltriethoxysilane (KH-550) is 1.21%, the content of the cyclosiloxane aminosilane is 78.33%, and the content of ethanol is 20.46%.
The reaction device is changed into a distillation device, brine with the temperature of minus 20 ℃ is adopted for condensation, distillation is carried out under the pressure of minus 0.01MPa, 454.2 g of ethanol and 1699.6 g of cyclosilazane are obtained, 62.1 g of material containing the catalyst is remained in the bottle, and the material is cooled and filtered, so as to obtain 3.3 g of catalyst and 58.8 g of silane polymer. The ethanol and silane polymer can be used for other industrial purposes, and the catalyst can be recycled.
The content of the cyclic silicon-nitrogen aminosilane detected by gas chromatography is 99.6%, and the molar yield of the cyclic silicon-nitrogen aminosilane product is 96.9%.
Example 5
10.0mol (2223.6 g) of aminoethyl-aminopropyltrimethoxysilane (KH-792) is added into a 3L three-neck flask, 2.0 g of zinc powder and 0.2 g of sodium methoxide are added, stirring is started after feeding is finished, the stirring speed is 150 rpm, the kettle is heated to 65 ℃ for heat preservation reaction for 3 hours, and then the crude product solution in the flask is taken and used for detecting the content by gas chromatography, wherein the aminoethyl-aminopropyltrimethoxysilane (KH-792) content is 0.84%, the cyclic silicon nitrogen aminosilane content is 85.05%, and the methanol content is 14.11%.
The reaction device is changed into a distillation device, brine with the temperature of 20 ℃ below zero is adopted for condensation, distillation is carried out under the pressure of 0.01MPa, 316.4 g of methanol and 1859.2 g of cyclosilazane are obtained, 50.2 g of materials containing the catalyst are remained in the bottle, and the materials are cooled and filtered to obtain 3.1 g of the catalyst and 47.1 g of the silane polymer. The methanol and silane polymer can be used for other industrial purposes, and the catalyst can be recycled.
The content of the cyclic silicon-nitrogen amino-silane is 99.5 percent by gas chromatography detection, and the molar yield of the cyclic silicon-nitrogen amino-silane product is 97.6 percent.
Comparative example 1
Adding 2.0mol (442.7 g) of aminopropyltriethoxysilane (KH-550) into a 1L three-neck flask, adding 0.3 g of nickel powder, after the feeding is finished, opening the stirring, wherein the stirring speed is 150 rpm, raising the temperature of a kettle to 75 ℃, keeping the temperature, reacting for 3 hours, taking a crude product solution in the flask, and detecting the content by using a gas chromatograph, wherein the content of the aminopropyltriethoxysilane (KH-550), the content of the cyclosiloxane aminosilane and the content of ethanol are 54.26 percent; keeping the temperature for reacting for 4 hours, and detecting the content of the crude product solution in the flask by using a gas chromatograph, wherein the content of aminopropyltriethoxysilane (KH-550), the content of cyclosilazane-aminosilane (CSA-CSA) and the content of ethanol are respectively 38.67%, 48.57% and 12.76%;
comparative example 2
Adding 2.0mol (442.7 g) of aminopropyltriethoxysilane (KH-550) into a 1L three-neck flask, adding 0.02 g of sodium ethoxide, after the feeding is finished, opening the stirring, wherein the stirring speed is 150 rpm, raising the temperature of the kettle to 75 ℃, keeping the temperature, reacting for 3 hours, taking a crude product solution in the flask, and detecting the content by using a gas chromatograph, wherein the content of the aminopropyltriethoxysilane (KH-550), the content of the cyclosiloxane aminosilane and the content of ethanol are 91.46%, 6.76% and 1.78%; keeping the temperature for reacting for 4 hours, and then taking the crude solution in the flask, and detecting the content by gas chromatography, wherein the content of aminopropyltriethoxysilane (KH-550), the content of cyclosiloxantronesilane and the content of ethanol are 82.62%, 13.76% and 3.62%, respectively.
Claims (1)
1. A synthetic method of cyclic silicon nitrogen amino silane is characterized in that: it comprises the following steps:
1) putting aminosilane into a reaction container, and adding a transition metal catalyst accounting for 0.05-0.1% of the weight of the added aminosilane; then adding 10ppm to 100ppm of alkali catalyst based on the weight of the added aminosilane;
2) after the feeding is finished, heating to 65-80 ℃ at a stirring speed of 120-150 rpm, and then carrying out heat preservation reaction for 3-4 hours to obtain a crude product of the cyclic silicon-nitrogen aminosilane;
3) distilling the crude product of the cyclosilazane aminosilane by a distillation device under the pressure of-0.01 MPa to obtain a product of the cyclosilazane aminosilane;
the amino silane is aminopropyl triethoxysilane or aminoethyl-aminopropyl trimethoxysilane;
the transition metal catalyst is nickel powder or zinc powder;
the alkali catalyst is sodium methoxide or sodium ethoxide.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115427A (en) * | 1976-09-01 | 1978-09-19 | Dynamit Nobel Aktiengesellschaft | Method of preparing silicon-nitrogen compounds |
| JP2011162497A (en) * | 2010-02-12 | 2011-08-25 | Shin-Etsu Chemical Co Ltd | Cyclic silazane compound and method for producing the same |
| WO2016094186A1 (en) * | 2014-12-10 | 2016-06-16 | Gelest Technologies, Inc. | High speed moisture-cure hybrid siloxane/silsesquioxane-urethane and siloxane/silsesquioxane-epoxy systems with adhesive properties |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115427A (en) * | 1976-09-01 | 1978-09-19 | Dynamit Nobel Aktiengesellschaft | Method of preparing silicon-nitrogen compounds |
| JP2011162497A (en) * | 2010-02-12 | 2011-08-25 | Shin-Etsu Chemical Co Ltd | Cyclic silazane compound and method for producing the same |
| WO2016094186A1 (en) * | 2014-12-10 | 2016-06-16 | Gelest Technologies, Inc. | High speed moisture-cure hybrid siloxane/silsesquioxane-urethane and siloxane/silsesquioxane-epoxy systems with adhesive properties |
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