CN101723675A - Boron nitride ceramic organic precursor and preparation method thereof - Google Patents
Boron nitride ceramic organic precursor and preparation method thereof Download PDFInfo
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- CN101723675A CN101723675A CN200910308549A CN200910308549A CN101723675A CN 101723675 A CN101723675 A CN 101723675A CN 200910308549 A CN200910308549 A CN 200910308549A CN 200910308549 A CN200910308549 A CN 200910308549A CN 101723675 A CN101723675 A CN 101723675A
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Abstract
The invention discloses a boron nitride ceramic organic precursor and a preparation method thereof and relates to a ceramic organic precursor and a preparation method thereof, which solve the problems of poor thermal stability, low ceramic productivity, harsh preparation method condition and long production period of boron nitride ceramic polymer precursors at present. The structural formula of the boron nitride ceramic organic precursor is disclosed in the specification, wherein n is 1, 2 or 3. The preparation method comprises the following steps of: adding trichlorine borazane and aniline to toluene, stirring and filtering to remove precipitates; then heating filter liquor and preserving heat; and finally, decompressing and distilling to remove the toluene to obtain the boron nitride ceramic organic precursor. The boron nitride ceramic organic precursor can be used for preparing boron nitride ceramic fibers, films, foams, allotropes and powders.
Description
Technical field
The present invention relates to ceramic organic precursor body and preparation method thereof.
Background technology
Development along with the modern aerospace technology, the research and development of high performance composite have become at present one of emphasis of Materials science research in the world, be applicable in the research of enhancing body of advanced composite material in preparation, ceramic fiber receives much attention because of its excellent thermotolerance and dielectric properties, wherein boron nitride (boron nitride) ceramic fiber is compared with other ceramic fiber and is had the intensity height, the dielectric properties height, high temperature resistant, anti-oxidant, density is little, can process, self-lubricating and good thermal conductivity and the performance of wave, in inertia and oxidizing atmosphere, its oxidation resistance temperature is higher than carbon fiber, therefore, wide application is being arranged aspect the aerospace flight technology field, can be used as the anti-cover of ablating, radome, anti-NEUTRON PROTECTION cover and the parachute of reentrying, suit etc.The method for preparing at present boron nitride ceramics fibre is to prepare the polymeric preceramic body earlier, then the polymeric preceramic body heat is handled and obtained boron nitride ceramics fibre, the decomposition temperature of existing polymeric preceramic body is 60 ℃～120 ℃, poor heat stability, be unfavorable for melt-spinning, ceramic yield is 35～45%; The polymeric preceramic body in the preparation need prepolymerization under-20 ℃～-10 ℃ cold condition, polymerization under 150 ℃～250 ℃ temperature then, when polymerization time reached 15h～160h, manipulation require carried out the condition harshness in the vacuum system of exclusion of water and oxygen simultaneously.
Summary of the invention
The present invention is in order to solve present boron nitride ceramics polymeric preceramic body heat poor stability, is unfavorable for that melt-spinning, ceramic yield are low, and preparation method's condition harshness, the long defective of preparation cycle provide boron nitride ceramic organic precursor body and preparation method thereof.
The structural formula of boron nitride ceramic organic precursor body of the present invention is:
Structural formula of the present invention is that the preparation method of the boron nitride ceramic organic precursor body of I formula is prepared being filled with relative humidity＜1% and being filled with in the glove box of nitrogen of volume percent purity＞99.9% of 0.1MPa by following step: one, be 1: 0.3～1.5 to join in the analytically pure toluene in molar ratio with trichlorine boron azine and analytically pure aniline, at room temperature stir 2h～3h, remove by filter white precipitate then; Two, filtrate the joining of getting step 1 has in the reactor of cooling and reflux device, opens and stirs, and is warming up to 80 ℃～85 ℃ and keeps 10min～15min, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 30 ℃～45 ℃ conditions that step 3 obtains, obtain the boron nitride ceramic organic precursor body.
Trichlorine boron azine in the step 1 of the boron nitride ceramic organic precursor body that described preparation structural formula is the I formula prepares as follows: a, 3 grams～8 gram analytically pure ammonium chlorides and the analytically pure toluene of 400mL are joined in the reactor with cooling and reflux device; B, feed boron trichloride gas under protection of nitrogen gas, the flow of control boron trichloride gas is opened and is stirred at 0.1L/min～0.4L/min, is warming up to 105 ℃～125 ℃ and keeps 10h, obtains liquid-solid mixture; C, remove by filter solid matter in the liquid-solid mixture; Filtrate underpressure distillation under 40 ℃～60 ℃ conditions after d, the step of learning from else's experience c handle removes toluene, obtains trichlorine boron azine.
℃ structural formula of the present invention is that the decomposition temperature of the boron nitride ceramic organic precursor body of I formula is 157.2 ℃, and Heat stability is good, ceramic yield are 52%; Structural formula be preparation method's the temperature of reaction of boron nitride ceramic organic precursor body of I formula in room temperature to 125 ℃ scope, the short (14h～17h) of simple, the mild condition of technology, preparation cycle.
The structural formula of boron nitride ceramic organic precursor body of the present invention can also for:
Structural formula of the present invention is that the preparation method of the boron nitride ceramic organic precursor body of II formula is prepared being filled with relative humidity＜1% and being filled with in the glove box of nitrogen of volume percent purity＞99.9% of 0.1MPa by following step: one, be 1: 1.5～3 to join in the analytically pure toluene in molar ratio with trichlorine boron azine and analytically pure aniline, at room temperature stir 3h～4h, remove by filter white precipitate then; Two, filtrate the joining of getting step 1 has in the reactor of cooling and reflux device, opens and stirs, and is warming up to 85 ℃～95 ℃ and keeps 15min～20min, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 30 ℃～45 ℃ conditions that step 3 obtains, obtain the boron nitride ceramic organic precursor body.
Structural formula of the present invention is that the decomposition temperature of the boron nitride ceramic organic precursor body of II formula is 163 ℃, and Heat stability is good, ceramic yield are 53.6%; Structural formula be preparation method's the temperature of reaction of boron nitride ceramic organic precursor body of II formula between room temperature to 125 ℃, total reaction times is 15h～18h, entire reaction course is carried out under normal pressure, the reaction conditions gentleness, the reaction times is short;
The structural formula of ℃ boron nitride ceramic organic precursor body of the present invention can also for:
Structural formula of the present invention be the preparation method of boron nitride ceramic organic precursor body of III formula by following step at relative humidity＜1% and be filled with in the glove box of nitrogen of volume percent purity＞99.9% of 0.1MPa and be prepared: be 1: 3～6 to join in the analytically pure toluene in molar ratio with trichlorine boron azine and analytically pure aniline one,, at room temperature stir 4h～5h, remove by filter white precipitate then; Two, filtrate the joining of getting step 1 has in the reactor of cooling and reflux device, opens and stirs, and is warming up to 95 ℃～100 ℃ and keeps 20min～30min, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 30 ℃～45 ℃ conditions that step 3 obtains, obtain the boron nitride ceramic organic precursor body.
Structural formula of the present invention is that the decomposition temperature of the boron nitride ceramic organic precursor body of III formula is 164.2 ℃, and Heat stability is good, ceramic yield are 55%; Structural formula be preparation method's the temperature of reaction of boron nitride ceramic organic precursor body of III formula between room temperature to 125 ℃, total reaction times is 17h～18.5h, entire reaction course is carried out under normal pressure, the reaction conditions gentleness, the reaction times is short.
Description of drawings
Fig. 1 is the infrared spectra of boron nitride ceramics organic precursor in the embodiment one; Fig. 2 is the TG/DTG curve of boron nitride ceramics organic precursor in the embodiment one; Fig. 3 is the XRD figure of gained trichlorine boron azine in the embodiment 35.
Embodiment
Embodiment one: the structural formula of boron nitride ceramic organic precursor body is in (referring to Fig. 1 and Fig. 2) present embodiment:
In the present embodiment infrared spectra of boron nitride ceramic organic precursor body as shown in Figure 1, as can be seen from Figure 1, at 3446cm
-1, 3223cm
-1And 812cm
-1The vibration of the corresponding N-H key of the absorption peak that the place occurs; At 753cm
-1The vibration of the corresponding B-N key of the absorption peak that the place occurs; At 1408cm
-1And 696cm
-1The vibration of the corresponding B-N key of the absorption peak that the place occurs; At 1064cm
-1The absorption peak that the place occurs is the vibration of B-Cl key; At 1613cm
-1The absorption peak that the place occurs is the characteristic absorbance of phenyl ring; At 500cm
-1The absorption peak that the place occurs is the vibration of N-H key on the phenyl ring, meets the structural formula of boron nitride ceramic organic precursor body
The TG/DTG curve of the boron nitride ceramic organic precursor body of present embodiment as shown in Figure 2, as can be seen from Figure 2 the decomposition temperature of boron nitride ceramic organic precursor body is 157.2 ℃, Heat stability is good.
The ceramic yield of the boron nitride ceramic organic precursor body of present embodiment is according to its TG/DTG curve calculation, the initial mass of the quality/polymkeric substance after 1000 ℃ of thermal treatments of ceramic yield=polymkeric substance, the ceramic yield of present embodiment gained boron nitride ceramic organic precursor body is 52%.
Embodiment two: in the present embodiment structural formula be the preparation method of boron nitride ceramic organic precursor body of I formula by following step at relative humidity＜1% and be filled with in the glove box of nitrogen of volume percent purity＞99.9% of 0.1MPa and be prepared: be 1: 0.3～1.5 to join in the analytically pure toluene in molar ratio with trichlorine boron azine and analytically pure aniline one,, at room temperature stir 2h～3h, remove by filter white precipitate then; Two, filtrate the joining of getting step 1 has in the reactor of cooling and reflux device, opens and stirs, and is warming up to 75 ℃～85 ℃ and keeps 10min～20min, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 30 ℃～45 ℃ conditions that step 3 obtains, obtain the boron nitride ceramic organic precursor body.
The structural formula of present embodiment is that preparation method's the temperature of reaction of the boron nitride ceramic organic precursor body of I formula is that 75 ℃～85 ℃, preparation time are 3h～5h, the preparation temperature of the trichlorine boron azine in the step 1 is that 105 ℃～125 ℃, preparation time are 11h～12h hour, so the temperature of reaction of present embodiment is between room temperature to 125 ℃, total preparation time is 14h～17h, entire reaction course is carried out under normal pressure, the reaction conditions gentleness, the reaction times is short.It is the boron nitride ceramic organic precursor body of 50Pas that the preparation method of the boron nitride ceramic organic precursor body of present embodiment can obtain the falling ball method viscosity of temperature under 45 ℃ of conditions, is fit to draw fibre product.
Embodiment three: what present embodiment and embodiment two were different is: the trichlorine boron azine in the step 1 prepares as follows: a, 3 grams～8 analytically pure ammonium chlorides of gram and the analytically pure toluene of 400mL are joined in the reactor with cooling and reflux device; B, feed boron trichloride gas under protection of nitrogen gas, the flow of control boron trichloride gas is opened and is stirred at 0.1L/min～0.4L/min, is warming up to 105 ℃～125 ℃ and keeps 10h, obtains liquid-solid mixture; C, remove by filter solid matter in the liquid-solid mixture; Filtrate underpressure distillation under 40 ℃～60 ℃ conditions after d, the step of learning from else's experience c handle removes toluene, obtains colourless acicular trichlorine boron azine crystal.Other is identical with embodiment two.
Embodiment four: present embodiment and embodiment two or threes' difference is: trichlorine boron azine and analytically pure aniline are 1: 0.5～1.2 in molar ratio in the step 1.Other is identical with embodiment two or three.
Embodiment five: the difference of present embodiment and embodiment two to four is: trichlorine boron azine and analytically pure aniline are 1: 0.9 in molar ratio in the step 1.Other is identical with embodiment two to four.
Embodiment six: the difference of present embodiment and embodiment two to five is:
Churning time in the step 1 is 2.2h～2.8h.Other is identical with embodiment two to five.
Embodiment seven: the difference of present embodiment and embodiment two to six is: the churning time in the step 1 is 2.5h.Other is identical with embodiment two to six.
Embodiment eight: the difference of present embodiment and embodiment two to seven is: 78 ℃～83 ℃ of the temperature in the step 2.Other is identical with embodiment two to seven.
Embodiment nine: the difference of present embodiment and embodiment two to eight is: 80 ℃ of the temperature in the step 2.Other is identical with embodiment two to eight.
Embodiment ten: the difference of present embodiment and embodiment two to nine is: the soaking time in the step 2 is 12min～18min, and other is identical with embodiment two to nine.
Embodiment 11: the difference of present embodiment and embodiment two to ten is: the soaking time in the step 2 is 15min, and other is identical with embodiment two to ten.
Embodiment 12: the difference of present embodiment and embodiment two to 11 is: trichlorine boron azine and analytically pure aniline are 1: 08 in molar ratio in the step 1, and churning time is 2.6h; 84 ℃ of temperature in the step 2, soaking time are 17min, and other step is identical with embodiment two to 11 with parameter.
The preparation method's of the boron nitride ceramic organic precursor body of present embodiment temperature of reaction is that 84 ℃, preparation time are 3.5h, the temperature of reaction of trichlorine boron azine is that 105 ℃～125 ℃, preparation time are 11h～12h hour, this shows, the temperature of reaction of present embodiment is between room temperature to 125 ℃, and under normal pressure, carry out, mild condition, total preparation time only are 14.5h～15.5h, and the reaction times is short.It is the boron nitride ceramic organic precursor body of 50Pas that the preparation method of the boron nitride ceramic organic precursor body of present embodiment can obtain the falling ball method viscosity of temperature under 45 ℃ of conditions, this boron nitride ceramic organic precursor body in nitrogen atmosphere, temperature is that 1000 ℃, pressure are that thermal treatment has prepared boron nitride ceramics fibre under the condition of 1.5MPa.
Embodiment 13: the structural formula of boron nitride ceramic organic precursor body is in the present embodiment:
The decomposition temperature of the boron nitride ceramic organic precursor body of present embodiment is 163 ℃, Heat stability is good; The ceramic yield of present embodiment gained boron nitride ceramic organic precursor body is 53.6%.
Embodiment 14: in the present embodiment structural formula be the preparation method of boron nitride ceramic organic precursor body of II formula by following step at relative humidity＜1% and be filled with in the glove box of nitrogen of volume percent purity＞99.9% of 0.1MPa and be prepared: be 1: 1.5～3 to join in the analytically pure toluene in molar ratio with trichlorine boron azine and analytically pure aniline one,, at room temperature stir 3h～4h, remove by filter white precipitate then; Two, filtrate the joining of getting step 1 has in the reactor of cooling and reflux device, opens and stirs, and is warming up to 85 ℃～95 ℃ and keeps 15min～25min, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 30 ℃～45 ℃ conditions that step 3 obtains, obtain the boron nitride ceramic organic precursor body.
The preparation process of the trichlorine boron azine in the present embodiment step 1 is identical with the preparation process of trichlorine boron azine in the embodiment three.
The preparation method's of the boron nitride ceramic organic precursor body of present embodiment temperature of reaction is that 85 ℃～95 ℃, preparation time are 4h～6h, the preparation temperature of the trichlorine boron azine in the step 1 is that 105 ℃～125 ℃, reaction times are 11h～12h hour, so the temperature of reaction of present embodiment is between room temperature to 125 ℃, total reaction times is 15h～18h, entire reaction course is carried out under normal pressure, the reaction conditions gentleness, the reaction times is short.It is 45 ℃ of boron nitride ceramic organic precursor bodies that the falling ball method viscosity under the condition is 260Pas that the preparation method of the boron nitride ceramic organic precursor body of present embodiment can obtain temperature, is fit to preparation film or foam article.
Embodiment 15: what present embodiment and embodiment 14 were different is: trichlorine boron azine and analytically pure aniline are 1: 1.7～2.7 in molar ratio in the step 1.Other is identical with embodiment 14.
Embodiment 16: the difference of present embodiment and embodiment 14 or 15 is: trichlorine boron azine and analytically pure aniline are 1: 2.1 in molar ratio in the step 1.Other is identical with embodiment 14 or 15.
Embodiment 17: the difference of present embodiment and embodiment 14 to 16 is: the churning time in the step 1 is 3.2h～3.8h.Other is identical with embodiment 14 to 16.
Embodiment 18: the difference of present embodiment and embodiment 14 to 17 is: the churning time in the step 1 is 3.5h.Other is identical with embodiment 14 to 17.
Embodiment 19: the difference of present embodiment and embodiment 14 to 18 is: 88 ℃～93 ℃ of the temperature in the step 2.Other is identical with embodiment 14 to 18.
Embodiment 20: the difference of present embodiment and embodiment 14 to 19 is: 90 ℃ of the temperature in the step 2.Other is identical with embodiment 14 to 19.
Embodiment 21: the difference of present embodiment and embodiment 14 to 20 is: the soaking time in the step 2 is 17min～23min, and other is identical with embodiment 14 to 20.
Embodiment 22: the difference of present embodiment and embodiment 14 to 21 is: the soaking time in the step 2 is 20min, and other is identical with embodiment 14 to 21.
Embodiment 23: the difference of present embodiment and embodiment 14 to 22 is: trichlorine boron azine and analytically pure aniline are 1: 2 in molar ratio in the step 1, and churning time is 3.6h; 92 ℃ of temperature in the step 2, soaking time are 21min, and other step is identical with embodiment 14 to 22 with parameter.
The preparation method's of the boron nitride ceramic organic precursor body of present embodiment temperature of reaction is that 92 ℃, reaction times are 4.6h, the preparation temperature of the trichlorine boron azine in the step 1 is that 105 ℃～125 ℃, reaction times are 11h～12h hour, so the temperature of reaction of present embodiment is between room temperature to 125 ℃, total reaction times is 15.6h～16.8h, entire reaction course is carried out at normal temperatures, the reaction conditions gentleness, the reaction times is short.It is 45 ℃ of boron nitride ceramic organic precursor bodies that the falling ball method viscosity under the condition is 260Pas that the preparation method of the boron nitride ceramic organic precursor body of present embodiment can obtain temperature.This boron nitride ceramic organic precursor body in nitrogen atmosphere, temperature is that 1000 ℃, pressure are that thermal treatment has prepared boron nitride ceramics film or foam article under the condition of 1.5MPa.
Embodiment 24: the structural formula of present embodiment boron nitride ceramic organic precursor body is:
The decomposition temperature of the boron nitride ceramic organic precursor body of present embodiment is 164.2 ℃, Heat stability is good; The ceramic yield of present embodiment gained boron nitride ceramic organic precursor body is 55%.
Embodiment 25: in the present embodiment structural formula be the preparation method of boron nitride ceramic organic precursor body of III formula by following step at relative humidity＜1% and be filled with in the glove box of nitrogen of volume percent purity＞99.9% of 0.1MPa and be prepared: be 1: 3～6 to join in the analytically pure toluene in molar ratio with trichlorine boron azine and analytically pure aniline one,, at room temperature stir 4h～5h, remove by filter white precipitate then; Two, filtrate the joining of getting step 1 has in the reactor of cooling and reflux device, opens and stirs, and is warming up to 95 ℃～100 ℃ and keeps 20min～30min, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 30 ℃～45 ℃ conditions that step 3 obtains, obtain the boron nitride ceramic organic precursor body.
The preparation process of the trichlorine boron azine in the present embodiment step 1 is identical with the preparation process of trichlorine boron azine in the embodiment three.
The preparation method's of the boron nitride ceramic organic precursor body of present embodiment temperature of reaction is 95 ℃～100 ℃, preparation time is 5h～6.5h, the preparation temperature of the trichlorine boron azine in the step 1 is 105 ℃～125 ℃, reaction times is 11h～12h hour, so the temperature of reaction of present embodiment is between room temperature to 125 ℃, total reaction times is 6h～18.5h, and entire reaction course does not need vacuum condition, the reaction conditions gentleness, the reaction times is short.It is 45 ℃ of boron nitride ceramic organic precursor bodies that the falling ball method viscosity under the condition is 500Pas that the preparation method of the boron nitride ceramic organic precursor body of present embodiment can obtain temperature, this boron nitride ceramic organic precursor body in nitrogen atmosphere, temperature is that 1000 ℃, pressure are that thermal treatment has prepared the boron nitride ceramics film under the condition of 1.5MPa.
Embodiment 26: the difference of present embodiment and embodiment 25 is: trichlorine boron azine and analytically pure aniline are 1: 3.2～5.7 in molar ratio in the step 1.Other is identical with embodiment 25.
Embodiment 27: the difference of present embodiment and embodiment 25 or 26 is: trichlorine boron azine and analytically pure aniline are 1: 4.5 in molar ratio in the step 1.Other is identical with embodiment 25 or 26.
Embodiment 28: the difference of present embodiment and embodiment 25 to 27 is: the churning time in the step 1 is 4.2h～4.8h.Other is identical with embodiment 25 to 27.
Embodiment 29: the difference of present embodiment and embodiment 25 to 28 is: the churning time in the step 1 is 4.5h.Other is identical with embodiment 25 to 28.
Embodiment 30: the difference of present embodiment and embodiment 25 to 29 is: the temperature in the step 2 is 96 ℃～99 ℃.Other is identical with embodiment 25 to 29.
The embodiment hentriaconta-: the difference of present embodiment and embodiment 25 to 30 is: the temperature in the step 2 is 97 ℃.Other is identical with embodiment 25 to 30.
Embodiment 32: present embodiment and embodiment 25 to the difference of hentriaconta-is: the soaking time in the step 2 is 22min～28min, and other is identical to hentriaconta-with embodiment 25.
Embodiment 33: the difference of present embodiment and embodiment 25 to 32 is: the soaking time in the step 2 is 25min, and other is identical with embodiment 25 to 32.
Embodiment 34: the difference of present embodiment present embodiment and embodiment 25 to 33 is: trichlorine boron azine in the step 1 and analytically pure aniline are that 1: 5, churning time are 4.4h in molar ratio; Temperature of reaction in the step 2 is that 98 ℃, soaking time are 27min.Other is identical with embodiment 25 to 33.
The preparation method's of the boron nitride ceramic organic precursor body of present embodiment temperature of reaction is that 98 ℃, reaction times are 6.5h, the preparation temperature of the trichlorine boron azine in the step 1 is 105 ℃～125 ℃, reaction times is 11h～12h hour, so the temperature of reaction of present embodiment is between room temperature to 125 ℃, total reaction times is 17h～18.5h, entire reaction course is carried out under normal pressure, the reaction conditions gentleness, and the reaction times is short.It is 45 ℃ of boron nitride ceramic organic precursor bodies that the falling ball method viscosity under the condition is 500Pas that the preparation method of the boron nitride ceramic organic precursor body of present embodiment can obtain temperature, with its in nitrogen atmosphere, temperature is 1000 ℃, thermal treatment had prepared boron nitride ceramics shaped piece and powder when pressure was 1.5MPa.
Embodiment 35: what (referring to Fig. 3) present embodiment and embodiment 25 to 34 were different is: the trichlorine boron azine in the step 1 prepares as follows: a, 5 analytically pure ammonium chlorides of gram and the analytically pure toluene of 400mL are joined in the reactor with cooling and reflux device; B, feed boron trichloride gas under protection of nitrogen gas, the flow of control boron trichloride gas is opened and is stirred at 0.2L/min, and heating makes temperature of charge rise to 110 ℃ to keep 10h, obtain liquid-solid mixture; C, remove by filter solid matter in the liquid-solid mixture; Filtrate underpressure distillation under 45 ℃ of conditions after d, the step of learning from else's experience c handle removes toluene, obtains colourless acicular trichlorine boron azine crystal.Other step is identical with embodiment 25 to 34 with parameter.
The trichlorine boron azine crystalline XRD figure institute of present embodiment gained is shown in Figure 3, contrast with PDF standard card, the crystal of gained and standard trichlorine boron azine crystalline similarity are 98% as can be known, and the crystal of hence one can see that present embodiment gained is a trichlorine boron azine crystal.
Embodiment 36: the boron nitride ceramic organic precursor body that present embodiment is respectively 50Pas, 260Pas, 500Pas by viscosity is by the mixed shown in the table 1, and the boron nitride ceramic organic precursor body that modulates different viscosity is to adapt to the requirement for preparing variant production.With the viscosity of falling ball method test boron nitride ceramic organic precursor body when temperature is 45 ℃, viscosity is that the boron nitride ceramic organic precursor body of 50Pas～150Pas is fit to draw fibre product, viscosity is that the boron nitride ceramic organic precursor body of 150Pas～300Pas is fit to preparation film or foam article, and viscosity is that the boron nitride ceramic organic precursor body of 300Pas～500Pas or vitreous state is fit to preparation shaped piece or powder.
The consumption of table 1 boron nitride ceramic organic precursor body range of viscosities and different viscosity boron nitride ceramic organic precursor body
| The range of viscosities of modulation back boron nitride ceramic organic precursor body | The mass percent of the boron nitride ceramic organic precursor body of 50Pas | Viscosity is the mass percent of the boron nitride ceramic organic precursor body of 260Pas | Viscosity is the mass percent of 500Pas boron nitride ceramic organic precursor body |
| ??50Pa·s～150Pa·s | ?60％～100％ | ??0％～30％ | ??0％～10％ |
| ??150Pa·s～300Pa·s | ?5％～20％ | ??70％～90％ | ??5％～10％ |
| ??300Pa·s～500Pa·s | ?0％～20％ | ??0％～10％ | ??70％～100％ |
Claims (10)
1. boron nitride ceramic organic precursor body is characterized in that the structural formula of boron nitride ceramic organic precursor body is:
2. the preparation method of boron nitride ceramic organic precursor body as claimed in claim 1, it is characterized in that the boron nitride ceramic organic precursor body is according to the following steps at relative humidity＜1% and be filled with in the glove box of nitrogen of volume percent purity＞99.9% of 0.1MPa and be prepared: one, be 1: 0.3～1.5 to join in the analytically pure toluene in molar ratio with trichlorine boron azine and analytically pure aniline, at room temperature stir 2h～3h, remove by filter white precipitate then; Two, filtrate the joining of getting step 1 has in the reactor of cooling and reflux device, opens and stirs, and is warming up to 75 ℃～85 ℃ and keeps 10min～20min, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 30 ℃～45 ℃ conditions that step 3 obtains, obtain the boron nitride ceramic organic precursor body.
3. the preparation method of boron nitride ceramic organic precursor body according to claim 2, the mol ratio that it is characterized in that trichlorine boron azine in the step 1 and analytically pure aniline are 1: 0.5～1.2, churning time is 2.2h～2.8h.
4. according to the preparation method of claim 2 or 3 described boron nitride ceramic organic precursor bodies, it is characterized in that temperature in the step 2 is that 78 ℃～83 ℃, soaking time are 12min～18min.
5. the preparation method of boron nitride ceramic organic precursor body according to claim 4 is characterized in that the trichlorine boron azine in the step 1 prepares as follows: a, 3 grams～8 gram analytically pure ammonium chlorides and the analytically pure toluene of 400mL are joined in the reactor with cooling and reflux device; B, feed boron trichloride gas under protection of nitrogen gas, the flow of control boron trichloride gas is opened and is stirred at 0.1L/min～0.4L/min, is warming up to 105 ℃～125 ℃ and keeps 10h, obtains liquid-solid mixture; C, remove by filter solid matter in the liquid-solid mixture; Filtrate underpressure distillation under 40 ℃～60 ℃ conditions after d, the step of learning from else's experience c handle removes toluene, obtains trichlorine boron azine.
6. boron nitride ceramic organic precursor body is characterized in that the structural formula of boron nitride ceramic organic precursor body is:
7. the preparation method of boron nitride ceramic organic precursor body as claimed in claim 6, it is characterized in that the boron nitride ceramic organic precursor body is according to the following steps at relative humidity＜1% and be filled with in the glove box of nitrogen of volume percent purity＞99.9% of 0.1MPa and be prepared: one, be 1: 1.5～3 to join in the analytically pure toluene in molar ratio with trichlorine boron azine and analytically pure aniline, at room temperature stir 3h～4h, remove by filter white precipitate then; Two, filtrate the joining of getting step 1 has in the reactor of cooling and reflux device, opens and stirs, and is warming up to 85 ℃～95 ℃ and keeps 15min～25min, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 30 ℃～45 ℃ conditions that step 3 obtains, obtain the boron nitride ceramic organic precursor body.
8. the preparation method of boron nitride ceramic organic precursor body according to claim 7, the mol ratio that it is characterized in that trichlorine boron azine in the step 1 and analytically pure aniline are 1: 1.7～2.7, churning time is 3.2h～3.8h; Temperature in the step 2 is that 88 ℃～92 ℃, soaking time are 17min～23min.
9. boron nitride ceramic organic precursor body is characterized in that the structural formula of boron nitride ceramic organic precursor body is:
10. the preparation method of boron nitride ceramic organic precursor body as claimed in claim 9, it is characterized in that the boron nitride ceramic organic precursor body is prepared being filled with relative humidity＜1% and being filled with in the glove box of nitrogen of volume percent purity＞99.9% of 0.1MPa according to the following steps: one, be 1: 3～6 to join in the analytically pure toluene in molar ratio with trichlorine boron azine and analytically pure aniline, at room temperature stir 4h～5h, remove by filter white precipitate then; Two, filtrate the joining of getting step 1 has in the reactor of cooling and reflux device, opens and stirs, and is warming up to 95 ℃～100 ℃ and keeps 20min～30min, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 30 ℃～45 ℃ conditions that step 3 obtains, obtain the boron nitride ceramic organic precursor body.
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| CN101948480A (en) * | 2010-09-25 | 2011-01-19 | 哈尔滨工业大学 | Boron nitride ceramic fiber organic precursor and preparation method thereof |
| CN103396125A (en) * | 2013-08-01 | 2013-11-20 | 哈尔滨工业大学（威海） | Preparation method for boron-carbon-nitrogen porous ceramic |
| CN109825900A (en) * | 2019-01-23 | 2019-05-31 | 中国人民解放军国防科技大学 | Preparation method of BCN nano ceramic fiber |
| CN113716581A (en) * | 2021-09-13 | 2021-11-30 | 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 |
| CN115477309A (en) * | 2022-09-01 | 2022-12-16 | 中国人民解放军国防科技大学 | High-ceramic-yield carbon-free boron nitride precursor anti-aqueous-oxygen modification method |
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| CN101172863B (en) * | 2007-10-19 | 2010-05-19 | 东华大学 | Method for producing boron-nitrogen ceramic fibre fore-runner body |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101948480A (en) * | 2010-09-25 | 2011-01-19 | 哈尔滨工业大学 | Boron nitride ceramic fiber organic precursor and preparation method thereof |
| CN103396125A (en) * | 2013-08-01 | 2013-11-20 | 哈尔滨工业大学（威海） | Preparation method for boron-carbon-nitrogen porous ceramic |
| CN103396125B (en) * | 2013-08-01 | 2014-07-02 | 哈尔滨工业大学（威海） | Preparation method for boron-carbon-nitrogen porous ceramic |
| CN109825900A (en) * | 2019-01-23 | 2019-05-31 | 中国人民解放军国防科技大学 | Preparation method of BCN nano ceramic fiber |
| CN109825900B (en) * | 2019-01-23 | 2021-03-02 | 中国人民解放军国防科技大学 | Preparation method of BCN (BCN-BCN) nano ceramic fiber |
| CN113716581A (en) * | 2021-09-13 | 2021-11-30 | 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 |
| CN115477309A (en) * | 2022-09-01 | 2022-12-16 | 中国人民解放军国防科技大学 | High-ceramic-yield carbon-free boron nitride precursor anti-aqueous-oxygen modification method |
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