CN115785453A - Continuous production method of polysilazane - Google Patents
Continuous production method of polysilazane Download PDFInfo
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- CN115785453A CN115785453A CN202211645904.0A CN202211645904A CN115785453A CN 115785453 A CN115785453 A CN 115785453A CN 202211645904 A CN202211645904 A CN 202211645904A CN 115785453 A CN115785453 A CN 115785453A
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Abstract
The invention provides a continuous production method of polysilazane, which uses methylhydrodichlorosilane or methylvinyldichlorosilane as a raw material to contact with ammonia gas flow in a continuous flow reactor for ammonolysis reaction, thereby obtaining a product. The method has the advantages of cheap and easily-obtained raw materials, simple and convenient operation, high automation degree, high synthesis yield, few byproducts, short reaction time and the like.
Description
Technical Field
The invention relates to the technical field of polysilazane production, in particular to a method for continuously preparing polysilazane by taking ammonia gas, methyl hydrogen dichlorosilane and methyl vinyl dichlorosilane as raw materials.
Background
Polysilazanes, i.e., polymers whose main chain is composed of Si-N bonds, are an important precursor for the preparation of Si-C-N ceramics. Since the bond angle difference (Δ θ =23 °) between Si and N atoms is smaller than the bond angle difference (Δ θ =36 °) between Si and O atoms, the ring formation tendency is smaller than that of polysiloxane, and the substituents are easily changed. Polysilazane as ceramic precursor has many advantages of high molecular weight, high viscosity, good adhesion, high temperature resistance, good elasticity and the like, and silicon nitride (Si) prepared from polysilazane 3 N 4 ) And silicon carbon nitride (Si) x N y C z ) The ceramic has excellent properties of high temperature resistance, wear resistance, corrosion resistance and the like, and can be used for preparing ceramic matrix composite materials(CMC) ultrahigh-temperature materials, bulk ceramics, catalysts, porous materials, lithium battery anodes, fillers, brake systems of high-speed trains and airplanes, transparent conductive films, and can also be used in the fields of ceramic bonding, ink-jet printing, multilayer connection of computer chips, oxidation resistance of silicone oil and silicone rubber, curing agents of silicone resin, sealing films of fuel cells, gas separation films and the like. The methyl hydrogen polysilazane is a polymer with a main chain of Si-N bond and a methyl or hydrogen atom linked on silicon, and the methyl vinyl polysilazane is a polymer with a main chain of Si-N bond and a vinyl or methyl group linked on silicon. They are the raw materials for preparing ceramic coatings and the functional ceramics.
At present, direct ammonolysis of dichlorosilane to polysilazane, ammonolysis of methylhydrodichlorosilane and methylvinyldichlorosilane to polysilazane, ring opening of hexaalkylcyclodisilazane by an organolithium reagent to polysilazane, ammonolysis of methylhydrodichlorosilane to polysilazane, and the like have been studied. Chenyiwang and the like obtain vinyl polysilazane by mixing a methyl vinyl dichlorosilane ammonolysis product, dimethyldichlorosilane and a methyl dichlorohydric silane ammonolysis product and carrying out heat preservation reaction for 24 hours at 200 ℃, and Chinese patent CN202210235109.8 is applied.
The method for producing polysilazane by purely using ammonolysis needs a large amount of solvent, is complex in separation, cannot realize continuous production, cannot control reaction process and is difficult to realize regulation and control of a polymer structure.
In view of the above, there is still a need in the art to develop a polysilazane production process that has a simple process, is environmentally friendly, can be used for continuous production, and can control the reaction process.
Disclosure of Invention
The invention aims to provide a polysilazane production process which is simple in process, environment-friendly, capable of realizing continuous production and controlling the reaction process.
In a first aspect of the invention, there is provided a process for the preparation of a methylhydropolysilazane stream, said process comprising the steps of:
(1) Evacuating in a continuous flow reactor;
(2) And (2) introducing a reaction raw material into the continuous flow reactor, contacting the ammonia gas flow with a methyl hydrogen dichlorosilane solution to carry out an ammonolysis reaction, separating and purifying to obtain methyl hydrogen polysilazane, or contacting the ammonia gas flow with a methyl vinyl dichlorosilane solution to carry out an ammonolysis reaction, and separating and purifying to obtain methyl vinyl polysilazane.
Preferably, the ammonolysis reaction time is from 0.01 seconds to 1200 seconds, preferably from 0.05 seconds to 750 seconds, more preferably from 0.1 seconds to 600 seconds, most preferably from 60 seconds to 180 seconds.
Preferably, the vacuum is applied to a pressure of 0.005MPa or less, preferably 0.001MPa or less.
Preferably, the pressure of the ammonia gas introduced is maintained at 0.1 to 1.0MPa, preferably 0.5MPa.
Preferably, the temperature of the ammonolysis reaction is 0 to 10 ℃, preferably 0 to 5 ℃.
Preferably, the solvent of the methylhydrogenodichlorosilane solution and the methylvinyldichlorosilane solution is at least one selected from the group consisting of toluene, xylene, ethylbenzene, n-hexane, n-octane, n-decane, cyclohexane, ethyl acetate, butyl acetate, t-butyl acetate, diethyl ether, n-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, petroleum ether, dichloromethane, chloroform, carbon tetrachloride, acetone, methyl butanone and ethyl butanone, or a combination thereof.
Preferably, the weight ratio of the solvent to the solute in the methylhydrodichlorosilane solution and the methylvinyldichlorosilane solution is 2-1, preferably 1.5-1:1.
preferably, ammonia gas and a methylhydrogen dichlorosilane solution are introduced into the continuous flow reactor, an excessive ammonia gas flow is contacted with the methylhydrogen dichlorosilane solution for ammonolysis reaction, and the methylhydrogen polysilazane is obtained after separation and purification, wherein the introduction speed of the methylhydrogen dichlorosilane solution is 1-100 kg/h, preferably 20-60 kg/h.
Preferably, ammonia gas and methyl vinyl dichlorosilane solution are introduced into the continuous flow reactor, excessive ammonia gas flow is contacted with the methyl vinyl dichlorosilane solution for ammonolysis reaction, and methyl vinyl polysilazane is obtained after separation and purification, wherein the introduction speed of the methyl vinyl dichlorosilane solution is 1-100 kg/h, preferably 20-60 kg/h.
Compared with the prior art, the invention has the advantages that:
1. when the methyl hydrogen polysilazane is prepared, the ammonolysis reaction is quickly carried out by adopting a continuous flow production process. The process has the characteristics of simple and single equipment, simple and safe operation, easily obtained raw materials, low cost, high yield and few three wastes, and the solvent is recycled in the reaction process, so that the production cost and the environmental pollution are greatly reduced, and the difficulty in separation and purification of products in post-treatment is reduced, so that the products are easier to refine and purify, and the purity of the products reaches more than 99%; the reaction time is short, and the efficiency of reaction equipment is greatly improved;
2. when the methyl vinyl polysilazane is prepared, the ammonolysis reaction is rapidly carried out by adopting a continuous flow production process. The process has the characteristics of simple and single equipment, simple and safe operation, easily obtained raw materials, low cost, high yield and few three wastes, and the solvent is recycled in the reaction process, so that the production cost and the environmental pollution are greatly reduced, and the difficulty in separation and purification of products in post-treatment is reduced, so that the products are easier to refine and purify, and the purity of the products reaches more than 99%; the reaction time is short, and the efficiency of the reaction equipment is greatly improved.
Drawings
FIG. 1 is a FT-IR spectrum of the IR spectrum of methylhydropolysilazane of example 1.
FIG. 2 shows the NMR spectrum of methylhydropolysilazane in example 1 1 H-NMR chart.
FIG. 3 is a FT-IR plot of the IR spectrum of methyl vinyl polysilazane from example 2.
FIG. 4 is the NMR spectrum of methylvinylpolysilazane from example 2 1 H-NMR chart.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
The reactor used in the present invention employs a commercially available continuous flow reactor. During the reaction, the reactants are pumped or pumped in to react.
As used herein, the term "contacting reagent a with reagent B" means that reagent a (liquid or gas phase) and reagent B (liquid or gas phase) are separately fed into a reactor, or reagent a (or reagent B) is placed in a reactor and then reagent B (or reagent a) is fed, and said "contacting" means that both materials coexist in a reactor in a very short time, i.e., a reaction time, relative to the time of contact of the materials in a conventional reaction, which is usually 0.1 second to 600 seconds, preferably 10 seconds to 360 seconds, more preferably 15 seconds to 180 seconds.
The production process specifically comprises the following steps:
1. continuous flow synthesis of methylhydropolysilazanes
And vacuumizing the continuous flow reactor, introducing excessive ammonia gas, and contacting the ammonia gas flow with the methylhydrogen dichlorosilane solution in the reactor to carry out ammonolysis reaction to obtain the methylhydrogen polysilazane. In this step, the residence time of the reaction is from 0.1 to 600 seconds, preferably from 60 to 180 seconds. After the reaction is finished, the solvent can be recycled. The synthesis of the methylhydropolysilazane by the method can greatly reduce the usage amount of the solvent.
2. Continuous flow synthesis of methyl vinyl polysilazanes
And vacuumizing the continuous flow reactor, introducing excessive ammonia gas, and contacting the ammonia gas flow with the methyl vinyl dichlorosilane solution in the reactor to carry out ammonolysis reaction to obtain the methyl vinyl polysilazane. In this step, the residence time of the reaction is from 0.1 to 600 seconds, preferably from 60 to 180 seconds. After the reaction is finished, the solvent can be recycled. The synthesis of methyl vinyl polysilazane by the above method can greatly reduce the amount of solvent used.
Example 1
Synthesis of methylhydropolysilazane: adding n-hexane/methylhydrogen dichlorosilane into a reaction kettle according to the mass ratio of 1/1, stirring for one hour at 0 ℃ to obtain a uniform methylhydrogen dichlorosilane solution, and transferring the uniform methylhydrogen dichlorosilane solution to a raw material solution storage tank for later use. The ammonia gas steel cylinder and the raw material solution storage tank are respectively connected with the continuous reactor through a delivery pump. And vacuumizing the continuous reactor to 0.005MPa, adjusting the pressure of an ammonia gas feed inlet to 0.5MPa, introducing excessive ammonia gas at 0 ℃, pumping a methylhydrogen dichlorosilane solution at the speed of 20 kg/h, and carrying out an aminolysis reaction for 120 seconds. And a discharge port of the continuous reactor is connected with a suction filtration device, filtrate subjected to suction filtration by the suction filtration device is rectified under the protection of nitrogen, so that a pure product and a solvent are obtained, the solvent n-hexane can be recycled, and the pure product methyl hydrogen polysilazane has the purity of 99% and the yield of 87%.
FIG. 1 is an FT-IR chart of the infrared spectrum of methylhydropolysilazane, which has the following characteristic peaks:
(N-H) Peak of Telescopic vibration =3387cm -1 ,(C-H)＝2950cm -1 (Si-H) stretching vibration peak =2121cm -1 ,(Si-CH 3 ) Deformation vibration peak =1391cm -1 、1252cm -1 (N-H) flexural vibration peak =1162cm -1 (Si-N) peak of stretching vibration =890cm -1 。
FIG. 2 shows NMR spectra of methylhydropolysilazane 1 H-NMR chart, characteristic peaks:
(Si-CH 3 ) 0.06-0.14ppm, (N-H) =0.14-0.40ppm, (Si-H) =4.40-4.80ppm, (solvent peak) =7.26ppm.
Example 2
Synthesis of methyl vinyl polysilazane: adding n-hexane/methyl vinyl dichlorosilane into a reaction kettle according to the mass ratio of 1/1, stirring for one hour at 0 ℃ to obtain a uniform methyl vinyl dichlorosilane solution, and transferring the uniform methyl vinyl dichlorosilane solution to a raw material solution storage tank for later use. The ammonia gas steel cylinder and the raw material solution storage tank are respectively connected with the continuous reactor through a delivery pump. And vacuumizing the continuous reactor to 0.005MPa, adjusting the pressure of an ammonia gas feed inlet to 0.5MPa, introducing excessive ammonia gas at 0 ℃, pumping 20 kg/h of methyl vinyl dichlorosilane solution, and carrying out ammonolysis reaction for 120 seconds. And a discharge port of the continuous reactor is connected with a suction filtration device, filtrate subjected to suction filtration by the suction filtration device is rectified under the protection of nitrogen, so that a pure product and a solvent are obtained, the normal hexane solvent can be recycled, the purity of the pure product methyl vinyl polysilazane is 99%, and the yield is 85%.
FIG. 3 is a FT-IR chart of the infrared spectrum of methyl vinyl polysilazane, which has the following characteristic peaks:
(N-H) Peak of stretching vibration =3385cm -1 ，(Si-CH＝CH 2 ) Peak of stretching vibration =1593cm -1 ，(Si-CH 3 ) Deformation vibration peak =1403cm -1 、1252cm -1 (N-H) flexural vibration peak =1150cm -1 (Si-N) peak of stretching vibration =891cm -1 .
FIG. 4 shows NMR spectra of methylvinylpolysilazanes 1 H-NMR chart, characteristic peaks:
(Si-CH 3 )＝0.09-0.23ppm，(N-H)＝0.23-ppm，(Si-CH＝CH 2 ) =5.54-6.38ppm, (solvent peak) =7.26ppm.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (9)
1. A method for continuously producing polysilazane, comprising the steps of:
(1) Evacuating in a continuous flow reactor;
(2) And (2) introducing a reaction raw material into the continuous flow reactor, contacting the ammonia gas flow with a methyl hydrogen dichlorosilane solution to carry out an ammonolysis reaction, separating and purifying to obtain methyl hydrogen polysilazane, or contacting the ammonia gas flow with a methyl vinyl dichlorosilane solution to carry out an ammonolysis reaction, and separating and purifying to obtain methyl vinyl polysilazane.
2. The process of claim 1, wherein the ammonolysis reaction time is from 0.01 seconds to 1200 seconds, preferably from 0.05 seconds to 750 seconds, more preferably from 0.1 seconds to 600 seconds, most preferably from 60 seconds to 180 seconds.
3. The method according to claim 1, characterized in that the vacuum is applied to below 0.005MPa, preferably below 0.001 MPa.
4. The method according to claim 1, wherein the ammonia gas is introduced at a pressure of 0.1 to 1.0MPa, preferably 0.5MPa.
5. The process according to claim 1, wherein the ammonolysis reaction temperature is between 0 and 10 ℃, preferably between 0 and 5 ℃.
6. The method of claim 1, wherein the solvent of the methylhydrodichlorosilane solution and the methylvinyldichlorosilane solution is selected from at least one of toluene, xylene, ethylbenzene, n-hexane, n-octane, n-decane, cyclohexane, ethyl acetate, butyl acetate, tert-butyl acetate, diethyl ether, n-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, petroleum ether, dichloromethane, chloroform, carbon tetrachloride, acetone, methyl butanone, and ethyl butanone, or a combination thereof.
7. The method of claim 1, wherein the weight ratio of solvent to solute in the methylhydrodichlorosilane solution and the methylvinyldichlorosilane solution is from 2 to 1, preferably from 1.5 to 1:1.
8. the method according to claim 1, wherein ammonia gas and the methylhydrogen dichlorosilane solution are introduced into the continuous flow reactor, the excess ammonia gas stream is contacted with the methylhydrogen dichlorosilane solution for ammonolysis reaction, and the methylhydrogen polysilazane is obtained after separation and purification, wherein the introduction speed of the methylhydrogen dichlorosilane solution is 1-100 kg/h, preferably 20-60 kg/h.
9. The process according to claim 1, wherein the aminolysis reaction is carried out by introducing ammonia gas and a solution of methylvinyldichlorosilane into a continuous flow reactor, contacting an excess ammonia gas stream with the solution of methylvinyldichlorosilane, and separating and purifying to obtain methylvinylpolysilazane, wherein the introduction rate of the solution of methylvinyldichlorosilane is 1 to 100 kg/h, preferably 20 to 60 kg/h.
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| KR20210045649A (en) * | 2019-10-17 | 2021-04-27 | 한국생산기술연구원 | Continuous Process for Synthesis of Polysilazane using a Carbon Dioxide as a solvent |
| CN115626937A (en) * | 2022-11-02 | 2023-01-20 | 宜昌泽美新材料有限公司 | Continuous production process of hexamethyldisilazane |
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- 2022-12-20 CN CN202211645904.0A patent/CN115785453A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150073436A (en) * | 2013-12-23 | 2015-07-01 | 오씨아이 주식회사 | Method of continuous manufacturing silicon nitride powder |
| CN104998598A (en) * | 2015-08-18 | 2015-10-28 | 李登仙 | Preparation device and preparation method for polysilazane |
| CN108676167A (en) * | 2018-04-03 | 2018-10-19 | 中国科学院化学研究所 | A kind of preparation facilities and method of polysilazane |
| CN109553777A (en) * | 2018-11-09 | 2019-04-02 | 中国科学院化学研究所 | A kind of room temperature curing agent of organosilicon material resistant to high temperature, preparation method and application |
| KR20210045649A (en) * | 2019-10-17 | 2021-04-27 | 한국생산기술연구원 | Continuous Process for Synthesis of Polysilazane using a Carbon Dioxide as a solvent |
| CN111303433A (en) * | 2020-03-04 | 2020-06-19 | 浙江理工大学 | Polysilazane with excellent spinning performance, preparation method thereof and melt spinning |
| CN115626937A (en) * | 2022-11-02 | 2023-01-20 | 宜昌泽美新材料有限公司 | Continuous production process of hexamethyldisilazane |
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