CN101182213A - Method for preparing silicon-boron-nitrogen ceramic fiber precursor - Google Patents
Method for preparing silicon-boron-nitrogen ceramic fiber precursor Download PDFInfo
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- CN101182213A CN101182213A CNA2007101705137A CN200710170513A CN101182213A CN 101182213 A CN101182213 A CN 101182213A CN A2007101705137 A CNA2007101705137 A CN A2007101705137A CN 200710170513 A CN200710170513 A CN 200710170513A CN 101182213 A CN101182213 A CN 101182213A
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Abstract
The invention relates to a preparation method of a silicon-boron-nitrogen ceramic fibre precursor. The high-temperature reaction of boron trichloride and ammonium chloride synthesizes as a borazine trichloride crystalloid; the product reacts with aliphatic alkylamine containing amidocyanogen or imino group under the low temperature and then reacts under the room temperature to obtain alkyl boride borazine (a). Silicon tetrachloride and hexamethyl silazane react under the room temperature and then react with boron trichloride to obtain Cl3Si-N-BCl2 (TADB) which then reacts with the aliphatic alkylamine containing the amidocyanogen or the imino group under the low temperature and then reacts under the room temperature to obtain the product (b); (a) and (b) are mixed and then heated to 130 DEG C to 250 DEG C to react to obtain a precursor polymer. The precursor has the good spinnability, and the pyrolysis product contains very little the element of carbon, which can provide the final silicon-boron-nitrogen fibre with good wave permeability.
Description
Technical field
The invention belongs to the silicon-boron-nitrogen ceramic fiber field, particularly relate to the preparation method of silicon-boron-nitrogen ceramic fiber precursor body.
Background technology
The silicon-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., be widely used in fields such as machinery, electronics metallurgy, chemical industry, aerospace, military engineering.
The silicon-boron-nitrogen pottery wherein silicon-boron-nitrogen ceramic fiber 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.
In general, the preparation of ceramic fiber can be adopted chemical Vapor deposition process (CVD), ultramicro powder sintering process or polymer precursor conversion method to wait to realize.Fiber fineness height, the mechanical property of CVD method preparation are good, but exist apparatus expensive, shortcoming that production efficiency is low, are unfavorable for realizing the large-batch industrial preparation; The fiber yarn footpath of ultramicro powder sintering process processing temperature height, preparation is thick, intensity is lower, oxidation-resistance is poor, and owing to added moulding, sintering aid, has introduced impurity in the fiber inevitably, and its dielectric properties also are affected.Under comparing, the polymer precursor conversion method has its special advantages: can form the composition of controlling ceramic fiber by the structure of controlling polymers presoma, thereby obtain having the material of estimated performance; Can adopt general polymerization thing spinning processing method to prepare precursor fibre, be converted into ceramic fiber through the pyrolysis under relatively low temperature of suitable not melt processed then.Because these characteristics, the presoma conversion method becomes the various ceramic fibers of present preparation method of greatest concern.The nitride ceramic fibre that at present adopts the presoma conversion method to succeed in developing in the world comprises nitride silicon based (Si
3N
4) fiber, Si-B-C-N base (SiBN
3C) fiber.External main research and development mechanism comprises the Domaine university of U.S. Dow Corning company, Japanese Tonen company, Japan Atomic Energy Research Institute, German Bayer company and France etc.Owing to abroad consider mainly that with the silicon-nitride-based ceramic fiber applications in high temperature structural composite material, so except that Tonen company product, the content of other several fibrous carbon elements is all higher, reality is the basic fiber of SiCN base or SiCNB.The existence of carbon has influenced the dielectric properties of material, makes these several fibers be not suitable for directly being used as saturating ripple fiber.And, the work of German M.Jansen seminar is only arranged abroad for the SiBN base pottery of carbon elements not, but the presoma that they obtain is insoluble molten, and can't the processing and preparing ceramic fiber.Earlier 1990s, Institute of Chemistry, Academia Sinica had once carried out the research that the polymer precursor conversion method prepares the SiCN base ceramic fibre, and draw out the nearly 1 meter precursor fibre of length with the self-control spinning equipment, behind not melt processed and high temperature pyrolysis, the ceramic fiber that obtains having certain intensity; The National University of Defense technology also once carried out relevant fundamental research with Shandong University.Needs at the research of heat resistance electromagnetic wave transparent material, utilize that Si-B-N system ablation property is good, the characteristics of good mechanical performance, carry out precursor process and prepare nitride based, the especially research of Si-B-N base ceramic fibre of high-performance, develop high comprehensive performance, the good Si-B-N base ceramic fibre of braiding property, to improve the performance level of China's high temperature resistant wave-permeable material, strengthen the ability of China's autonomous innovation aspect the special cermacis fiber research.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of silicon-boron-nitrogen ceramic fiber precursor 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, rises to room temperature reaction again and obtains boron substituted alkyl borazine (a).With obtaining Cl with boron trichloride reaction again after the reaction under silicon tetrachloride and the hexa methyl silazane room temperature
3Si-N-BCl
2(TADB), TADB reacts again with the aliphatic alkylamine that contains amido or imido grpup at low temperatures, rises to room temperature reaction again and obtains product (b).(a) mixed post-heating to 130 ℃～250 ℃ of reactions with (b), obtain preceramic polymer.This precursor has better spinnability, and contains few carbon in the split product, can make final silicon-boron-nitrogen fiber have good wave.
Chemical equation of the present invention is as follows:
1) reaction equation of preparation ring-type trichlorine boron azane
2) chemical equation of TCB and methylamine reaction
3) chemical equation of preparation TADB.
4) reaction equation of TADB and methylamine
5) be 2 and 4 mixed reaction equations.
The preparation method of a kind of silicon-boron-nitrogen ceramic fiber precursor 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);
(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;
(3) Cl
3Si-N-BCl
2(TADB) preparation
Silicon tetrachloride and hexa methyl silazane were at room temperature reacted 10～30 hours, be added drop-wise to again in the toluene solution of boron trichloride-10 ℃～0 ℃ down reaction 30min～150min obtain Cl
3Si-N-BCl
2(TADB);
(4) Cl
3Si-N-BCl
2(TADB) with the reaction of amine
TADB slowly is added drop-wise to the anhydrous toluene solution of the excessive aliphatic alkylamine that contains amido or imido grpup under-80 ℃～-70 ℃ violent stirring, after dripping, temperature is risen to-60 ℃～0 ℃, reacted 1～10 hour, rose to room temperature reaction again 10～20 hours;
(5) preceramic polymer is synthetic
(2) are removed precipitation with the product mixing after-filtration that (4) reaction obtains; the polymeric solution that obtains places reactor; accompanied by intense is stirred in 70 ℃～120 ℃ and removes residual toluene under the vacuum state; under the protection of nitrogen or argon gas, be warmed up to 130 ℃～250 ℃ of final synthesis temperatures then, reacted 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;
Containing the amido aliphatic alkylamine in the described step (2) is methylamine.
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;
The mol ratio of silicon tetrachloride and hexa methyl silazane reaction is 1: 4～10: 1 in the described step (3), and the mol ratio of reaction product and boron trichloride reaction is 1: 1～1: 5.
Filtration in the described step (5) is to carry out in the glove box that is full of nitrogen or argon gas;
Intensification in the described step (5) is to adopt the progressively extremely final synthesis temperature of linear temperature increase, and heat-up rate is 0.5～20 ℃/min.
Beneficial effect of the present invention:
(1) can obtain having the silicon-boron-nitrogen preceramic 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.
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).
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) lentamente 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.
Embodiment 3
The hexa methyl silazane (0.08mol) of 70g silicon tetrachloride (0.41mol) and 12.5g places the there-necked flask of 250ml together, at room temperature stirred 20 hours, the product that obtains is added dropwise under-40 ℃ in the flask of 500ml of the boron trichloride (1.39mol) that 163g is housed slowly.Drip the back temperature and rise to 0 ℃ of reaction 1 hour, rise to room temperature more slowly and so just obtained TADB.
Embodiment 4
In the anhydrous toluene solution of the methylamine that slowly is added drop-wise to 100ml under-78 ℃ of violent stirring, after dripping, temperature rises to 0 ℃, reacts 5 hours, rises to room temperature reaction again 10 hours with the TADB that obtains among the embodiment 3.
Embodiment 5
Embodiment 2 is removed precipitation with the product mixing after-filtration that embodiment 4 reactions obtain, the polymeric solution that obtains places the there-necked flask that has magnetic agitation of 250ml, mixing solutions being stirred and heated to 75 ℃ and removing remaining toluene of accompanied by intense under vacuum, obtain weak yellow liquid, reaction system progressively is warmed up to 180 ℃ in nitrogen then, kept 20 hours, weak yellow liquid gradually by the liquid thick solid that becomes at last that can not stir that becomes.
Claims (9)
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 TCB
With BCl
3With exsiccant inert nitrogen gas or argon gas slowly by being heated to 100 ℃～240 ℃ NH
4Cl powder, reaction generate ring-type trichlorine boron azane needle-like crystal;
(2) reaction of ring-type trichlorine boron azane and amine
Ring-type trichlorine boron azane is dissolved in the dry toluene, slowly drip the anhydrous toluene solution of the aliphatic alkylamine that contains amido or imido grpup under-80 ℃～-70 ℃ violent stirring, after dripping, temperature rises to-60 ℃～0 ℃, reacted 1～10 hour, rose to room temperature reaction again 10～20 hours.
(3) Cl
3Si-N-BCl
2The preparation of TADB
Silicon tetrachloride and hexa methyl silazane were at room temperature reacted 10～30 hours, be added drop-wise to then in the toluene solution of boron trichloride, react 30min～150min down at-10 ℃～0 ℃ and obtain Cl
3Si-N-BCl
2TADB.
(4) reaction of TADB and amine
TADB slowly is added drop-wise in the anhydrous toluene solution of the excessive aliphatic alkylamine that contains amido or imido grpup under-80 ℃～-70 ℃ violent stirring, after dripping, temperature is risen to-60 ℃～0 ℃, reacted 1～10 hour, rose to room temperature reaction again 10～20 hours.
(5) preceramic polymer is synthetic
(2) are removed precipitation with the product mixing after-filtration that (4) reaction obtains; the polymeric solution that obtains places reactor; accompanied by intense is stirred in 70 ℃～120 ℃ and removes residual toluene under the vacuum state; under the protection of nitrogen or argon gas, be warmed up to 130 ℃～250 ℃ of final synthesis temperatures, reacted 5～40 hours.
2. the preparation method of silicon-boron-nitrogen ceramic fiber precursor 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 silicon-boron-nitrogen ceramic fiber precursor 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 silicon-boron-nitrogen ceramic fiber precursor body according to claim 1 is characterized in that: 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.
5. the preparation method of silicon-boron-nitrogen ceramic fiber precursor body according to claim 1 is characterized in that: the aliphatic alkylamine that contains amido in the described step (2) is a methylamine.
6. the preparation method of silicon-boron-nitrogen ceramic fiber precursor 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.
7. the preparation method of silicon-boron-nitrogen ceramic fiber precursor body according to claim 1, it is characterized in that: the mol ratio of silicon tetrachloride and hexa methyl silazane reaction is 1: 4～10: 1 in the described step (3), and the mol ratio of reaction product and boron trichloride reaction is 1: 1～1: 5.
8. the preparation method of silicon-boron-nitrogen ceramic fiber precursor body according to claim 1 is characterized in that: the filtration in the described step (5) is to carry out in the glove box that is full of nitrogen or argon gas.
9. the preparation method of silicon-boron-nitrogen ceramic fiber precursor body according to claim 1 is characterized in that: the employing in the described step (5) is linear temperature increase progressively, and heat-up rate is 0.5～20 ℃/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913877A (en) * | 2010-08-13 | 2010-12-15 | 东华大学 | Method for preparing borosilazane ceramic fiber precursor |
| CN102503423A (en) * | 2011-11-22 | 2012-06-20 | 东华大学 | Preparation method of SiBNC bulk ceramics |
| CN102557645A (en) * | 2011-11-14 | 2012-07-11 | 中国人民解放军国防科学技术大学 | Boron-carbon-nitrogen ceramic fiber and preparation method thereof |
| CN102604108A (en) * | 2012-03-15 | 2012-07-25 | 中国科学院化学研究所 | Organic silicon binding agent and special silicon-boron-carbon-nitrogen polymer thereof |
| CN104974352A (en) * | 2015-06-24 | 2015-10-14 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of SiBCN ceramic precursor containing borazine structure |
| CN116178013A (en) * | 2023-01-12 | 2023-05-30 | 宁波杭州湾新材料研究院 | Preparation method of SiBN ceramic precursor with controllable silicon-boron atomic ratio |
-
2007
- 2007-11-16 CN CNB2007101705137A patent/CN100567210C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913877A (en) * | 2010-08-13 | 2010-12-15 | 东华大学 | Method for preparing borosilazane ceramic fiber precursor |
| CN102557645A (en) * | 2011-11-14 | 2012-07-11 | 中国人民解放军国防科学技术大学 | Boron-carbon-nitrogen ceramic fiber and preparation method thereof |
| CN102557645B (en) * | 2011-11-14 | 2013-04-10 | 中国人民解放军国防科学技术大学 | Boron-carbon-nitrogen ceramic fiber and preparation method thereof |
| CN102503423A (en) * | 2011-11-22 | 2012-06-20 | 东华大学 | Preparation method of SiBNC bulk ceramics |
| CN102604108A (en) * | 2012-03-15 | 2012-07-25 | 中国科学院化学研究所 | Organic silicon binding agent and special silicon-boron-carbon-nitrogen polymer thereof |
| CN102604108B (en) * | 2012-03-15 | 2013-11-06 | 中国科学院化学研究所 | Organic silicon binding agent and special silicon-boron-carbon-nitrogen polymer thereof |
| CN104974352A (en) * | 2015-06-24 | 2015-10-14 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of SiBCN ceramic precursor containing borazine structure |
| CN116178013A (en) * | 2023-01-12 | 2023-05-30 | 宁波杭州湾新材料研究院 | Preparation method of SiBN ceramic precursor with controllable silicon-boron atomic ratio |
| CN116178013B (en) * | 2023-01-12 | 2024-01-30 | 宁波杭州湾新材料研究院 | Preparation method of SiBN ceramic precursor with controllable silicon-boron atomic ratio |
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