CN102173398A - Low-molecular carbon-free polysilazane and liquid-phase synthesis method thereof - Google Patents
Low-molecular carbon-free polysilazane and liquid-phase synthesis method thereof Download PDFInfo
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- CN102173398A CN102173398A CN 201110007914 CN201110007914A CN102173398A CN 102173398 A CN102173398 A CN 102173398A CN 201110007914 CN201110007914 CN 201110007914 CN 201110007914 A CN201110007914 A CN 201110007914A CN 102173398 A CN102173398 A CN 102173398A
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Abstract
The invention discloses a low-molecular carbon-free polysilazane and a liquid-phase synthesis method thereof, and is characterized in that the low-molecular carbon-free polysilazane is liquid state, structurally contains Si-N, Si-H and N-H bonds and does not contains carbon or other foreign elements. The liquid-phase synthesis method comprises the following steps: (1) feeding organic solvents and halogenated silicane in a container which is provided with a raw material feed pipe, a gas pipe, a stirrer and a condenser; (2) introducing an excessive amount of hydronitrogen compounds into the container, standing for 0.5 to 7 hours, filtering in an inert atmosphere to obtain a clear solution; and (3) distilling under reduced pressure at room temperature or under heating to remove the organic solvents, to obtain a transparent solution. The silicon nitride ceramics produced by cracking the low-molecular carbon-free polysilazane are excellent in dielectric properties. The starting compounds for synthesis are easily available and low in price. The synthesis device has a simple structure, is convenient to operate and has good controllability. The synthetic product has a high purity and a high yield.
Description
Technical field
The present invention relates to a kind of polysilazane and synthetic method thereof and device, specifically, relate to the carbon-free polysilazane of a kind of low molecule and liquid-phase synthesis process and device.
Background technology
Silicon nitride (Si
3N
4) be the covalent linkage compound, belong to hexagonal system, two kinds of structures of α-crystal formation and beta-crystal are arranged.The chemical ingredients of two kinds of crystal formations is identical with density, all is hexahedrons.The c shaft length of different is α-crystal formation structure cell approximately is the twice of beta-crystal.Silicon nitride is a kind of important non-oxidized substance advanced ceramics material, has good comprehensive performances, as high strength, high rigidity, high temperature resistant, anti-thermal shock, self-lubricating or the like, therefore, silicon nitride has very wide application prospect in fields such as high-temperature structural material, high-performance bearing materials.
In addition, silicon nitride also has excellent dielectric properties, becomes one of preferred material of the saturating parts for wave of high Mach number guided missile.
In recent years,, adopt the radome of silicon nitride and nitride silicon based Composite Preparation high-performance guided missile, become the focus of each military power's research along with development of aviation and aerospace technology.
But because the Si-N key is the chemical bond of height covalency in the silicon nitride, bonding strength is very high, makes it be difficult to sintering.At present, the mode that adopts reaction sintering usually or add sintering aid is therein carried out the preparation of silicon nitride material, causes the material purity for preparing not high.As dielectric materials, purity is directly determining the dielectric properties of material, is a very crucial index.Therefore, explore the new preparation method of silicon nitride and matrix material thereof, be subjected to investigator's common concern.
The technology of precursor cracking conversion preparation stupalith provides effective way for the low temperature preparation of high purity silicon nitride.Yet, as the precursor of silicon nitride ceramics, often containing the alkyl of some amount in the structure of polysilazane, this electrical property to material can have a negative impact.Therefore, synthetic a kind of carbon-free polysilazane is the key of preparation high purity silicon nitride material.
Summary of the invention
The object of the present invention is to provide a kind of dielectric properties excellence, the carbon-free polysilazane of low molecule and liquid-phase synthesis process and device that synthesis technique is easy.
Purpose of the present invention is achieved by following technical solution:
The present invention's the low carbon-free polysilazane of molecule is liquid state, only contains Si-N, Si-H and N-H key in its structure, and molecular weight 104～360 is adjustable, not carbon containing or other impurity elements.
The present invention's carbon-free polysilazane synthetic method, selecting halogenated silanes for use is the silicon source, hydronitrogen is a nitrogenous source, and the two is placed organic solvent, thorough mixing, reaction generates target product.
The concrete operations step is as follows:
(1) in the container that material inlet pipe, airway, agitator and condenser are housed, add organic solvent and halogenated silanes by the material inlet pipe, start agitator and stir, make halogenated silanes be dissolved in organic solvent;
(2) in described container, feed the excess nitrogen hydrogen compound, under ℃ condition of normal temperature～110, leave standstill 0.5～7 hour (preferred 1-6 hour), under inert atmosphere protection, filter then, obtain settled solution;
(3) organic solvent is removed in underpressure distillation under normal temperature or heating condition, obtains transparent liquid.
Described organic solvent can be and is selected from a kind of in tetrahydrofuran (THF), diethylene glycol dimethyl ether, triethylene glycol dme, tetraethyleneglycol dimethyl ether, the pyridine or the mixture more than two kinds wherein.
Described halogenated silanes can be a chlorosilane, dihydro dichlorosilane, trichlorosilane, a silicon fluoride, dihydro two silicon fluorides, silicofluoroform, a bromo-silicane, dihydro two bromo-silicanes, tribromosilane, an iodine silane, dihydro diiodo-silane or triiodo silane.
Described hydronitrogen can be ammonia or hydrazine.
Described inert atmosphere preferred nitrogen.
Implement the device of described carbon-free polysilazane synthetic method, comprise the container that has silicon source material inlet pipe, nitrogenous source material inlet pipe, agitator, silicon source material inlet pipe is provided with the rare gas element air-guide branch pipe, and nitrogenous source material inlet pipe one side is provided with condenser, and described container places temperature controlled water bath.
Use the present invention's the silicon nitride ceramics that the carbon-free polysilazane cracking of molecule is made that hangs down, the dielectric properties excellence, specific inductivity can reach 2.5～4.0; Synthetic method has following advantage: the starting compound source is wide, and cheap, synthesizer is simple, and is easy to operate, and controllability is good, synthetic product purity height, productive rate height.
To synthetic product, through Fourier's Infrared spectroscopy (FTIR), mass spectroscopy (MS), nmr analysis (H
1-NMR), and the high-temperature split product of synthetic product carried out X-ray diffraction analysis (XRD), find that the synthetic product has higher purity, cleavable is highly purified silicon nitride ceramics.
Description of drawings
Fig. 1 is a kind of laboratory synthesizer of the carbon-free polysilazane of the present invention;
Fig. 2 is the infrared spectrogram of the carbon-free polysilazane of the embodiment of the invention 1 synthetic;
Fig. 3 is the carbon-free polysilazane of the embodiment of the invention 1 synthetic
1The H-NMR nmr spectrum;
Fig. 4 is the XRD spectra of the carbon-free polysilazane split product of the embodiment of the invention 1 synthetic.
Embodiment
The invention will be further described below in conjunction with embodiment.
The carbon-free polysilazane synthesizer structure that each embodiment described below uses is referring to Fig. 1.It comprises the container 5 that has silicon source material inlet pipe 1, nitrogenous source material inlet pipe 3, agitator 2, silicon source material inlet pipe 1 is provided with rare gas element air-guide branch pipe 6, nitrogenous source material inlet pipe 3 one sides are provided with and are used to cool off the condenser 4 that reacts the gas that produces, and container 5 places temperature controlled water bath 7.The condensing agent that condenser uses is the room temperature tap water.
Embodiment 1
(1) checks the synthesizer resistance to air loss,, vacuumize, charge into nitrogen to container 5, carry out repeatedly three times, the air in the displacement container 5 by rare gas element air-guide branch pipe 6 with whole device thorough drying;
(2) add tetrahydrofuran (THF) and trichlorosilane by silicon source material inlet pipe 1 to container 5, wherein tetrahydrofuran (THF) is excessive; Start agitator 2 and stir, make trichlorosilane be dissolved in tetrahydrofuran (THF) fully;
(3) start condenser 4, feed excessive ammonia by nitrogenous source material inlet pipe 3 in container 5, by temperature controlled water bath 7 container 5 is heated to 60 ℃, left standstill 3 hours, reaction finishes, and filters under inert atmosphere protection, obtains settled solution;
(4) solvents tetrahydrofurane is removed in underpressure distillation at normal temperatures, obtains transparent liquid, i.e. carbon-free polysilazane of the present invention.Productive rate about 48%.
The carbon-free polysilazane infrared spectrogram that present embodiment synthesizes, 1H-NMR nmr spectrum are respectively referring to Fig. 2,3; Only contain Si-N, Si-H and N-H key in its structure, not carbon containing or other impurity elements.The XRD spectra of the split product of described carbon-free polysilazane (being silicon nitride ceramics) is referring to Fig. 4; Its specific inductivity is 3.4.
Embodiment 2:
(1) with embodiment 1 step (1);
(2) add pyridine and dihydro dichlorosilane to container 5, wherein pyridine is excessive; Starting agitator 2 stirs;
(3) start condenser 4, feed excessive ammonia in container, left standstill at normal temperatures 6 hours, reaction finishes; Under inert atmosphere protection, filter, obtain settled solution;
(4) the solvent pyridine is removed in underpressure distillation under normal temperature or heating condition, obtains transparent liquid, carbon-free polysilazane promptly of the present invention.Productive rate about 70%.
The specific inductivity of the split product (being silicon nitride ceramics) of the carbon-free polysilazane that present embodiment is synthetic is 3.3.
Embodiment 3
(1) with embodiment 1 step (1);
(2) add a triethylene glycol dme and a chlorosilane to container 5, wherein solvent triethylene glycol dme is excessive; Starting agitator 2 stirs;
(3) start condenser 4, feed excessive hydrazine in container 5, be heated to 100 ℃, left standstill 1 hour, reaction finishes; Under inert atmosphere protection, filter, obtain settled solution;
(4) the solvent pyridine is removed in underpressure distillation under normal temperature or heating condition, obtains transparent liquid, carbon-free polysilazane promptly of the present invention.Productive rate about 75%.
The specific inductivity of the split product (being silicon nitride ceramics) of the carbon-free polysilazane that present embodiment is synthetic is 3.6.
Claims (7)
1. the carbon-free polysilazane of low molecule is characterized in that, is liquid state, only contains Si-N, Si-H and N-H key in its structure, and molecular weight 104～360 is adjustable, not carbon containing or other impurity elements.
2. the liquid-phase synthesis process of the carbon-free polysilazane of low molecule as claimed in claim 1 is characterized in that the concrete operations step is as follows:
(1) in the container that material inlet pipe, airway, agitator and condenser are housed, add organic solvent and halogenated silanes, start agitator and stir;
(2) in described container, feed the excess nitrogen hydrogen compound, left standstill 0.5～7 hour, under inert atmosphere protection, filter then, obtain settled solution;
(3) organic solvent is removed in underpressure distillation under normal temperature or heating condition, obtains transparent liquid.
3. according to the liquid-phase synthesis process of the carbon-free polysilazane of the described low molecule of claim 2, it is characterized in that described organic solvent is to be selected from a kind of in tetrahydrofuran (THF), diethylene glycol dimethyl ether, triethylene glycol dme, tetraethyleneglycol dimethyl ether, the pyridine or the mixture more than two kinds wherein.
4. according to the liquid-phase synthesis process of claim 2 or the carbon-free polysilazane of 3 described low molecules, it is characterized in that described halogenated silanes is a chlorosilane, dihydro dichlorosilane, trichlorosilane, a silicon fluoride, dihydro two silicon fluorides, silicofluoroform, a bromo-silicane, dihydro two bromo-silicanes, tribromosilane, an iodine silane, dihydro diiodo-silane or triiodo silane.
5. according to the liquid-phase synthesis process of claim 2 or the carbon-free polysilazane of 3 described low molecules, it is characterized in that described institute hydronitrogen is ammonia or hydrazine.
6. according to the liquid-phase synthesis process of the carbon-free polysilazane of the described low molecule of claim 4, it is characterized in that described hydronitrogen is ammonia or hydrazine.
7. device of implementing the described carbon-free polysilazane synthetic method of claim 2, it is characterized in that, comprise the container that has silicon source material inlet pipe, nitrogenous source material inlet pipe and agitator, silicon source material inlet pipe is provided with the rare gas element air-guide branch pipe, nitrogenous source material inlet pipe one side is provided with condenser, and described container places temperature controlled water bath.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012214290A1 (en) | 2012-08-10 | 2014-02-13 | Evonik Industries Ag | Process for the coupled preparation of polysilazanes and trisilylamine |
| CN104072781A (en) * | 2014-07-03 | 2014-10-01 | 中国科学院化学研究所 | Perhydropolysilazane with controllable ratio of SiH2 to SiH1 in molecular structure, hydrophobic transparent high-hardness coating prepared by perhydropolysilazane and synthesis method of perhydropolysilazane |
| DE102013209802A1 (en) | 2013-05-27 | 2014-11-27 | Evonik Industries Ag | Process for the coupled preparation of trisilylamine and polysilazanes having a molecular weight of up to 500 g / mol |
| 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 |
| CN112500573A (en) * | 2020-12-11 | 2021-03-16 | 湖南博望碳陶有限公司 | Organic polysilazane and large-scale production method thereof |
| US11124876B2 (en) | 2015-03-30 | 2021-09-21 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Si-containing film forming precursors and methods of using the same |
| US11699584B2 (en) | 2015-03-30 | 2023-07-11 | L'Air Liquide, Société Anonyme pour l'Edute ed l'Exploitation des Procédés Georges Claude | Si-containing film forming precursors and methods of using the same |
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| CN1390223A (en) * | 1999-11-12 | 2003-01-08 | 基昂公司 | Novel silizane and/or polysilazane compounds and methods of making |
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| CN1390223A (en) * | 1999-11-12 | 2003-01-08 | 基昂公司 | Novel silizane and/or polysilazane compounds and methods of making |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014023470A1 (en) | 2012-08-10 | 2014-02-13 | Evonik Industries Ag | Process for coupled preparation of polysilazanes and trisilylamine |
| DE102012214290A1 (en) | 2012-08-10 | 2014-02-13 | Evonik Industries Ag | Process for the coupled preparation of polysilazanes and trisilylamine |
| WO2014191058A1 (en) | 2013-05-27 | 2014-12-04 | Evonik Industries Ag | Method for the coupled production of trisilylamine and polysilazanes having a molar mass of up to 500 g/mol |
| DE102013209802A1 (en) | 2013-05-27 | 2014-11-27 | Evonik Industries Ag | Process for the coupled preparation of trisilylamine and polysilazanes having a molecular weight of up to 500 g / mol |
| CN104072781B (en) * | 2014-07-03 | 2016-11-09 | 中国科学院化学研究所 | SiH in a kind of molecular structure2and SiH1the controlled Perhydropolysilazane of ratio and hydrophobic transparent high hardness spray coating prepared therefrom and synthetic method thereof |
| CN104072781A (en) * | 2014-07-03 | 2014-10-01 | 中国科学院化学研究所 | Perhydropolysilazane with controllable ratio of SiH2 to SiH1 in molecular structure, hydrophobic transparent high-hardness coating prepared by perhydropolysilazane and synthesis method of perhydropolysilazane |
| US11124876B2 (en) | 2015-03-30 | 2021-09-21 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Si-containing film forming precursors and methods of using the same |
| US11699584B2 (en) | 2015-03-30 | 2023-07-11 | L'Air Liquide, Société Anonyme pour l'Edute ed l'Exploitation des Procédés Georges Claude | Si-containing film forming precursors and methods of using the same |
| US11820654B2 (en) | 2015-03-30 | 2023-11-21 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Si-containing film forming precursors and methods of using the same |
| CN104998598A (en) * | 2015-08-18 | 2015-10-28 | 李登仙 | Preparation device and preparation method for polysilazane |
| CN104998598B (en) * | 2015-08-18 | 2017-09-15 | 福建省博涵能源科技有限公司 | A kind of preparation facilities of polysilazane and preparation method thereof |
| 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 |
| CN112500573A (en) * | 2020-12-11 | 2021-03-16 | 湖南博望碳陶有限公司 | Organic polysilazane and large-scale production method thereof |
| CN112500573B (en) * | 2020-12-11 | 2022-08-26 | 湖南博望碳陶有限公司 | Organic polysilazane and large-scale production method thereof |
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Application publication date: 20110907 |