CN101172863B - Method for producing boron-nitrogen ceramic fibre fore-runner body - Google Patents
Method for producing boron-nitrogen ceramic fibre fore-runner body Download PDFInfo
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- CN101172863B CN101172863B CN200710047281A CN200710047281A CN101172863B CN 101172863 B CN101172863 B CN 101172863B CN 200710047281 A CN200710047281 A CN 200710047281A CN 200710047281 A CN200710047281 A CN 200710047281A CN 101172863 B CN101172863 B CN 101172863B
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Abstract
The invention relates to a preparation method of boron-nitrogen ceram fibre precursor, and the method comprises the steps as follows: synthesizing boron chloride azane crystal through high temperature reaction of boron trichloride and ammonium chloride, making the product of the reaction above and the fat alkylamine containing amidocyanogen or imidogen react under low temperature, then reacting under room temperature, and heating to 130 to 250 DEG C to obtain the precursor polymer. The precursor has good spinnability, and the crack production has small carbon element, so as to make the final boron-nitrogen fibre have good wave-transparent performance.
Description
Technical field
The invention belongs to the boron-nitrogen ceramic fibre field, particularly relate to the preparation method of boron-nitrogen ceramic fibre fore-runner body.
Background technology
Boron nitrogen pottery is a kind of high performance non-oxygen stupalith, have high temperature resistant, corrosion-resistant and the good interface characteristic, can be used as instrument, grinding tool, thermal structure spare, wear resistant corrosion resistant spare, sealing member and biomaterial etc. are widely used in machinery, electronics metallurgy, chemical industry, aerospace, fields such as military engineering.
Boron nitrogen pottery wherein boron-nitrogen ceramic fibre have high temperature resistant (3000 ℃ of inert atmospheres) but, resistance to chemical attack, good characteristics such as dielectric properties are good, electrical insulating property good, the good intercept neutrons of thermal conductivity.
The preparation method of boron-nitrogen ceramic fibre mainly contains two kinds, and a kind of is chemical transformation, and another kind is the precursor conversion method.The former is a gas and solid heterogeneous reaction because of nitrogenizing reaction, is difficult to make the fiber of homogeneous, the synthetic main employing latter of high performance boron nitrogen fiber.Prepare the method for boron nitride fibre owing to there is the problem that removes of carbon with precursor the earliest, and the pure boron nitrogen pottery of difficult acquisition, US Pat.4 afterwards, 581,468 have introduced the method that a kind of organo-boron polymer prepares boron nitride fibre, are to react acquisition by ammonia (ammonolysis) and three chloro-trialkyl silicomethane-borazoles (ring compound), because the method initial compounds is difficult to preparation, cause this method to involve great expense, be difficult to carry out.There were many methods to prepare boron-nitrogen compound afterwards again, for example R T PAINE etc. is at Chem Rev.1990.90,73～91 elaborations are synthesized preceramic polymer with organic compound such as boron azane, C K Narula etc. are at Chem Mater.1990.2, with trichlorine boron azane or 2-dimethylin-4,6-dichloro boron azane at room temperature reacts synthetic precursor in the dichloromethane solution with hexa methyl silazane, at patent FR-A2 in 384～389, pass through functional group [B (NR in 695,645
1R
2)-NR
3-]
3Thermal polycondensation and obtain precursor, R wherein
1, R
2And R
3The expression or identical or different hydrogen bases or alkyl.Top these polymkeric substance of telling about are suitable for preparing the coating of powder or some forms, but with these polymer manufacture more the complexity film particularly fiber be very difficult.
It mainly is because its chemical structure is the reticulated structure of crosslinked trackless that precursor be difficult to form fiber, and after the course of processing in these structural defectives can cause breakage and some weakness of fiber, and cause final mechanical property also poor.
T Wideman etc. are at Chem Mater.1998.10, other preceramic polymer of some that set forth in 412～421 that they find relatively is fit to obtain boron nitrogen fiber, and the preceramic polymer of this suitable melt-spinning may be to obtain by improved poly-boron azo-cycle alkane and dialkylamine or hexa methyl silazane reaction.
The Bernard S. group of France is carrying out a large amount of work aspect the structure design of the precursor polymer of ring-type trichlorine boron azane (TCB); utilize ring-type trichlorine boron azane and methylamine reaction (Macromolecules.2007.40; 1018～1027); polymerization under protection of inert gas then; melt-spinning obtains high performance BN fiber through the pyroprocessing of ammonia and nitrogen.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of boron-nitrogen ceramic fibre fore-runner body, this method synthesizes trichlorine borazine crystal by boron trichloride and ammonium chloride pyroreaction, product reacts at low temperatures with the aliphatic alkylamine that contains amido or imido grpup, rise to room temperature reaction for some time again, be heated to 130 ℃～250 ℃ reactions then, get final product.The precursor of present method preparation has better spinnability, and contains few carbon in the split product, can make final boron nitrogen fiber have good wave.
The preparation method of a kind of boron-nitrogen ceramic fibre fore-runner body of the present invention, reaction process is as follows:
The preparation method of a kind of boron-nitrogen ceramic fibre fore-runner body of the present invention comprises the following steps:
(1) preparation of ring-type trichlorine boron azane
With BCl
3With exsiccant inert nitrogen gas or argon gas slowly by being heated to 100 ℃～240 ℃ NH
4The Cl solid, reaction generates the needle-like crystal of ring-type trichlorine boron azane (TCB) in special reaction unit (Fig. 1);
(2) reaction of ring-type trichlorine boron azane and amine
Ring-type trichlorine boron azane is dissolved in the dry toluene, under-80 ℃～-70 ℃ violent stirring, slowly drip the anhydrous toluene solution of the excessive aliphatic alkylamine that contains amido or imido grpup, after dripping, temperature rises to-60 ℃～0 ℃, reacted 1～10 hour, rose to room temperature reaction again 10～20 hours, filter and remove white flocks, precipitate 1～8 time with the dry toluene flushing, filtrate and extraction liquid mix the back and remove part toluene under the room temperature high vacuum;
(3) the poly-boron azane of precursor is synthetic
The polymeric solution that is obtained by (2) is in reactor, and the vacuum accompanied by intense stirs down and removes residual toluenes at 70 ℃～120 ℃, is warmed up to 130 ℃～250 ℃ of final synthesis temperatures under the protection of nitrogen or argon gas, reacts 5～40 hours.
NH in the described step (1)
4In vacuum drying oven, dried by the fire 1～30 hour under 50 ℃～180 ℃ earlier before Cl uses, remove moisture wherein, and be crushed to 0～200 order;
BCl in the described step (1)
3With NH
4The mol ratio of Cl is 1: 1～1: 10;
The aliphatic alkylamine that contains amido or imido grpup in the described step (2) is that aliphatic chain length is the aliphatic alkylamine of 1～5 carbon atom, the mol ratio of aliphatic alkylamine and ring-type trichlorine boron azane is 1: 1～10: 1, and the volume ratio of aliphatic alkylamine and dry toluene is 2: 1～1: 5;
Filtration in the described step (2) is to carry out in the glove box that is full of nitrogen or argon gas;
Intensification in the described step (3) is that progressively linear temperature increase is to final synthesis temperature, and heat-up rate is 0.5～20 ℃/min.
Beneficial effect of the present invention:
(1) can obtain having the boron-nitrogen polymer of linear structure, help becoming fine, and the better mechanical property of fiber;
(2) ceramic fiber precursor that makes in the ammonia atmosphere, be heated to 900 ℃ of resulting products through ultimate analysis as can be known the content of carbon be less than 0.03%, can reach good wave;
(3) by product that forms in the reaction process-alkyl ammomium chloride solid is to form in the synthesized micromolecule monomer stage, separates from reaction system easily.
Description of drawings
Fig. 1 is the special reaction unit figure of preparation ring-type trichlorine boron azane;
Fig. 2-the 1st, the infrared spectrum of ring-type trichlorine boron azane;
Fig. 2-the 2nd, the infrared spectrum of the precursor of TCB and methylamine reaction;
Fig. 2-the 3rd, the infrared spectrum of the precursor of TCB and dimethylamine reaction;
Fig. 2-the 4th, the infrared spectrum of the precursor that TCB and methylamine and dimethylamine all react.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Ammonium chloride is put into vacuum drying oven dry by the fire 12 hours down to remove moisture wherein at 110 ℃, be crushed to after the cooling and reinstall in the U-shaped pipe below 200 orders, to install and couple together by Fig. 1, feed exsiccant nitrogen, the U-shaped pipe that ammonium chloride is housed is heated to 165 ℃～175 ℃, keeps 2 hours to remove the steam in the device.Feed boron trichloride gas after 2 hours, in another U-shaped pipe, just occurred the acicular crystal of white at once, Here it is ring-type trichlorine boron azane (TCB).Fig. 2-1 is the infrared spectrum of ring-type trichlorine boron azane.
Embodiment 2
7.7g TCB (41.9mmol) be dissolved in the dry toluene there-necked flask of the 250ml that places-78 ℃, be accompanied by the intensive magnetic agitation drips excessive 35ml anhydrous methylamine (338.7mmol) slowly in flask anhydrous toluene solution (volume ratio of methylamine and toluene is 1: 1), the cotton-shaped methyl ammonia chloride precipitation with regard to adularescent generates immediately.After methylamine drips, stirring reaction 1 hour, temperature rises to-40 ℃ and stirred 5 hours, and temperature stops after 20 hours stirring rising to stirring at room afterwards.At this moment many white flockss are arranged in the solution, in being filled with the glove box of nitrogen, will precipitate removal, the anhydrous toluene solution washing precipitation of usefulness 50ml 3 times by filtering.Filtrate and extraction liquid mix the back and remove part toluene under the room temperature high vacuum.
Embodiment 3
7.7g TCB (41.9mmol) be dissolved in the dry toluene there-necked flask of the 250ml that places-78 ℃, be accompanied by the intensive magnetic agitation drips excessive 35ml anhydrous dimethyl amine (346.5mmol) slowly in flask anhydrous toluene solution (volume ratio of dimethylamine and toluene is 1: 1), the cotton-shaped dimethyl chlorination amine precipitation with regard to adularescent generates immediately.After dimethylamine drips, stirring reaction 1 hour, temperature rises to-40 ℃ and stirred 5 hours, and temperature stops after 20 hours stirring rising to stirring at room afterwards.At this moment many white flockss are arranged in the solution, in being filled with the glove box of nitrogen, will precipitate removal, the anhydrous toluene solution washing precipitation of usefulness 50ml 3 times by filtering.Filtrate and extraction liquid mix the back and remove part toluene under the room temperature high vacuum.
Embodiment 4
7.7g TCB (41.9mmol) be dissolved in the dry toluene there-necked flask of the 250ml that places-78 ℃, be accompanied by the anhydrous toluene solution (volume ratio of dimethylamine and toluene is 1: 1) of the anhydrous dimethyl amine (83.85mmol) of the intensive magnetic agitation drips excessive 5ml anhydrous methylamine (41.97mmol) slowly in flask anhydrous toluene solution (volume ratio of methylamine and toluene is 1: 1) and 10ml, cotton-shaped methyl ammonia chloride and the alkyl dimethyl ammonium chloride precipitation with regard to adularescent generates immediately.After methylamine drips, stirring reaction 1 hour, temperature rises to-40 ℃ and stirred 5 hours, and temperature stops after 20 hours stirring rising to stirring at room afterwards.At this moment many white flockss are arranged in the solution, in being filled with the glove box of nitrogen, will precipitate removal, the anhydrous toluene solution washing precipitation of usefulness 50ml three times by filtering.Filtrate and extraction liquid mix the back and remove part toluene under the room temperature high vacuum.
Embodiment 5
7.7g TCB (41.9mmol) be dissolved in the toluene there-necked flask of the 250ml that places-78 ℃, be accompanied by the intensive magnetic agitation drips excessive 15ml anhydrous methylamine (83.85mmol) slowly in flask the anhydrous toluene solution (volume ratio of methylamine and toluene is 1: 1) and the anhydrous toluene solution (volume ratio of dimethylamine and toluene is 1: 1) of 8ml anhydrous dimethyl amine (41.97mmol), cotton-shaped ammonio methacrylate and the alkyl dimethyl ammonium chloride precipitation with regard to adularescent generates immediately.After methylamine drips, stirring reaction 1 hour, temperature rises to-40 ℃ and stirred 5 hours, and temperature stops after 20 hours stirring rising to stirring at room afterwards.At this moment many white flockss are arranged in the solution, in being filled with the glove box of nitrogen, will precipitate removal, the anhydrous toluene solution washing precipitation of usefulness 50ml three times by filtering.Filtrate and extraction liquid mix the back and remove part toluene under the room temperature high vacuum.
Embodiment 6
Put into the there-necked flask that has magnetic agitation of 250ml according to embodiment 2 prepared polymeric solutions, mixing solutions is accompanied by intensive in a vacuum and is stirred and heated to 75 ℃ of remaining toluene of removal, obtain milky white liquid, be reflected at then and progressively be warmed up to 180 ℃ in the nitrogen, kept 20 hours, white liquid gradually the liquid thick faint yellow solid that becomes at last that can not stir that becomes arranged.Fig. 2-2 is the infrared spectrum of the precursor of TCB and methylamine reaction.
Embodiment 7
Put into the there-necked flask that has magnetic agitation of 250ml according to embodiment 3 prepared polymeric solutions, mixing solutions is accompanied by intensive in a vacuum and is stirred and heated to 75 ℃ of remaining toluene of removal, obtain yellow liquid, be reflected at then and progressively be warmed up to 180 ℃ in the nitrogen, kept 20 hours, yellow liquid gradually the liquid thick solid that becomes at last that can not stir that becomes arranged.The infrared spectrum of the precursor of Fig. 2-3TCB and dimethylamine reaction.
Embodiment 8
Put into the there-necked flask that has magnetic agitation of 250ml according to embodiment 4 prepared polymeric solutions, mixing solutions is accompanied by intensive in a vacuum and is stirred and heated to 75 ℃ of remaining toluene of removal, obtain weak yellow liquid, be reflected at then and progressively be warmed up to 180 ℃ in the nitrogen, kept 20 hours, weak yellow liquid gradually the liquid thick solid that becomes at last that can not stir that becomes arranged.
Embodiment 9
Put into the there-necked flask that has magnetic agitation of 250ml according to embodiment 5 prepared polymeric solutions, mixing solutions is accompanied by intensive in a vacuum and is stirred and heated to 75 ℃ of remaining toluene of removal, obtain weak yellow liquid, be reflected at then and progressively be warmed up to 180 ℃ in the nitrogen, kept 20 hours, weak yellow liquid gradually the liquid thick solid that becomes at last that can not stir that becomes arranged.The infrared spectrum of the precursor that Fig. 2-4 reacts for TCB and methylamine and dimethylamine.
Claims (6)
1. the preparation method of a boron-nitrogen ceramic fibre fore-runner body comprises the following steps:
(1) preparation of ring-type trichlorine boron azane
With BCl
3With exsiccant inert nitrogen gas or argon gas slowly by being heated to 100 ℃～240 ℃ NH
4The Cl solid, reaction generates ring-type trichlorine boron azane TCB needle-like crystal in special reaction unit;
(2) reaction of ring-type trichlorine boron azane and amine
Ring-type trichlorine boron azane is dissolved in the dry toluene, under-80 ℃～-70 ℃ violent stirring, slowly drip the anhydrous toluene solution of the excessive aliphatic alkylamine that contains amido or imido grpup, after dripping, temperature rises to-60 ℃～0 ℃, reacted 1～10 hour, rose to room temperature reaction again 10～20 hours, filter and remove precipitation, precipitate 1～8 time with the dry toluene flushing, filtrate and extraction liquid mix the back and remove part toluene under the room temperature high vacuum;
Wherein, the aliphatic alkylamine that contains amido or imido grpup is that aliphatic chain length is the aliphatic alkylamine of 1～5 carbon atom;
(3) the poly-boron azane of precursor is synthetic
The polymeric solution that is obtained by (2) is in reactor, and the vacuum accompanied by intense stirs down and removes residual toluenes at 70 ℃～120 ℃, is warmed up to 130 ℃～250 ℃ of final synthesis temperatures under the protection of nitrogen or argon gas, reacts 5～40 hours.
2. the preparation method of boron-nitrogen ceramic fibre fore-runner body according to claim 1 is characterized in that: NH in the described step (1)
4In vacuum drying oven, dried by the fire 1～30 hour under 50 ℃～180 ℃ earlier before Cl uses, remove moisture wherein, and be crushed to 0～200 order.
3. the preparation method of boron-nitrogen ceramic fibre fore-runner body according to claim 1 is characterized in that: BCl in the described step (1)
3With NH
4The mol ratio of Cl is 1: 1～1: 10.
4. the preparation method of boron-nitrogen ceramic fibre fore-runner body according to claim 1, it is characterized in that: the mol ratio of aliphatic alkylamine and ring-type trichlorine boron azane is 1: 1～10: 1 in the described step (2), and the volume ratio of aliphatic alkylamine and dry toluene is 2: 1～1: 5.
5. the preparation method of boron-nitrogen ceramic fibre fore-runner body according to claim 1, it is characterized in that: the filtration in the described step (2) is to carry out in the glove box that is full of nitrogen or argon gas.
6. the preparation method of boron-nitrogen ceramic fibre fore-runner body according to claim 1 is characterized in that: the intensification in the described step (3) is that progressively linear temperature increase is to final synthesis temperature, and heat-up rate is 0.5～20 ℃/min.
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| CN101723675B (en) * | 2009-10-21 | 2012-07-25 | 哈尔滨工业大学 | Boron nitride ceramic organic precursor and preparation method thereof |
| CN101948480B (en) * | 2010-09-25 | 2012-06-06 | 哈尔滨工业大学 | Boron nitride ceramic fiber organic precursor and preparation method thereof |
| CN112341627B (en) * | 2020-11-25 | 2022-04-19 | 中国人民解放军国防科技大学 | Method for synthesizing novel spinnable polyboroazane precursor in one pot |
| CN113716581B (en) * | 2021-09-13 | 2023-03-14 | 中国人民解放军国防科技大学 | High-ceramic-yield carbon-free boron nitride precursor and synthesis method thereof |
| CN115806435B (en) * | 2023-02-09 | 2023-06-16 | 山东工业陶瓷研究设计院有限公司 | Preparation method of boron nitride powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4581468A (en) * | 1985-05-13 | 1986-04-08 | Ultrasystems, Inc. | Boron nitride preceramic polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4581468A (en) * | 1985-05-13 | 1986-04-08 | Ultrasystems, Inc. | Boron nitride preceramic polymers |
Non-Patent Citations (2)
| Title |
|---|
| sylvain等.Design of a Series of Preceramic B-Tri(methylamino)borazine-Based Polymers as Fiber Precursors: Architecture, ThermalBehavior, and Melt-Spinnability.Macromolecules 2007年第40期.2007,(2007年第40期),全文. |
| sylvain等.Design of a Series of Preceramic B-Tri(methylamino)borazine-Based Polymers as Fiber Precursors: Architecture, ThermalBehavior, and Melt-Spinnability.Macromolecules 2007年第40期.2007,(2007年第40期),全文. * |
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