CN101948480B - Boron nitride ceramic fiber organic precursor and preparation method thereof - Google Patents
Boron nitride ceramic fiber organic precursor and preparation method thereof Download PDFInfo
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- ZJXQOUSRUSCCOF-UHFFFAOYSA-N CCC(B(NB(NCC=C)N1)NB1N(CC=C)C(B(NB(NCC=C)N1)NB1Cl)(CC)CC)(CC)N(B1NSNB(NCC=C)N1)CC=C Chemical compound CCC(B(NB(NCC=C)N1)NB1N(CC=C)C(B(NB(NCC=C)N1)NB1Cl)(CC)CC)(CC)N(B1NSNB(NCC=C)N1)CC=C ZJXQOUSRUSCCOF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a boron nitride ceramic fiber organic precursor and a preparation method thereof, relating to the boron nitride ceramic fiber organic precursor and the preparation method thereof and solving the problems of low molecular weight of the traditional boron nitride ceramic fiber organic precursor prepared from borazole trichlorine and phenylamine and poor wire-forming property during spinning. The structural formula of the boron nitride ceramic fiber organic precursor is described in the specification, wherein n is an integer between 10 and 13. The preparation method comprises the steps of: adding the borazole trichlorine and the phenylamine into methylbenzene and stirring, then filtering to obtain filtrate, refluxing the filtrate at a temperature of 60-90 DEG C, decompressing and distilling for removing the methylbenzene, and heating in a drying oven to obtain the boron nitride ceramic fiber organic precursor. The number-average molar mass of the boron nitride ceramic fiber organic precursor is 2000-2750; the boron nitride ceramic fiber organic precursor is capable of melting and spinning, and has the advantages of convenient operation and good wire-forming property; and the boron nitride ceramic fiber organic precursor can be thermally treated to obtain pure and boron nitride fibers with better crystallization and hexagonal structure, and can be used for preparing the boron nitride fibers.
Description
Technical field
The present invention relates to boron nitride ceramic organic precursor body and preparation method thereof.
Background technology
SP 1 (BN) pottery is the development along with hi-tech, particularly the development of space industry technology and a kind of high-performance engineering stupalith of receiving publicity gradually.SP 1 is 3000 ℃ of distillations, is 2 times of room temperature 1800 ℃ intensity, in inert atmosphere 2800 ℃ softening; Have high heat resistance, thermal conductivity>=530W/mK is the maximum material of thermal conductivity in the stupalith; SP 1 and Fe, Cu, Al, Pb, rare earth metal, precious metal, semiconductor material, mineral acid, alkali do not react; Have superior corrosion resistance, thermal expansivity is lower, has only 2 * 10
6/ ℃, the volume specific resistance of SP 1 in the time of 25 ℃ be 10
14Ω cm, 2000 ℃ reach 10
3Ω cm has good insulation performance performance, low frictional coefficient and good processability.Because boron nitride ceramics has above-mentioned premium properties, so its application is also very extensive: six side BN can be used to make advanced refractory materials, TiB
2Spout, high frequency induction furnace liner, thermocouple protective casing and the high-temperature coatings etc. of the rod of the additive of polymkeric substance such as/BN composite ceramics, high temperature lubricant, transistorized heat-sealing siccative, resin, the heatshield material in the aerospace, pile neutron absorption, the structured material of reactor, crucible material, semiconductor packages radiating bottom plate, thrust chamber.
It is the organic precursor method method that the method for preparing boron nitride ceramic material is used more; Existing publication No. is that the Chinese patent of CN101723675A discloses the method for utilizing trichlorine boron azine and aniline to prepare the boron nitride ceramic material organic precursor method, and the molecular structural formula of the boron nitride ceramic organic precursor body of this method preparation is:
is 240～620 for the molecular weight of
these boron nitride ceramic organic precursor bodies perhaps; Molecular weight is lower; Be fit to preparation film and powder body material, and ropiness is poor when the preparation boron nitride fibre.
Summary of the invention
The present invention is low in order to solve existing boron nitride ceramic material organic precursor method molecular weight with trichlorine boron azine and aniline preparation, the problem of ropiness difference in spinning process, and boron nitride ceramics fibre organic precursor method and preparation method thereof is provided.
The structural formula of boron nitride ceramics fibre organic precursor method of the present invention is
wherein integer of n=10～13.
The preparation method of boron nitride ceramics fibre organic precursor method of the present invention is according to the following steps at relative humidity≤1% and be filled with in the glove box of nitrogen of purity>=99.9% (volume) of 0.1MPa and carry out: be 1: 0.5～1.5 to join in the toluene in molar ratio with trichlorine boron azine and allyl amine one; At room temperature stir 2h～4h, remove by filter white precipitate then; Filtrating the joining of two, getting step 1 has in the reactor drum of cooling and reflux device, opens and stirs, and is warming up to 60 ℃～90 ℃ and keeps 15h～28h, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 60 ℃～65 ℃ conditions that step 2 obtains; Four, will place temperature through the liquid form mixt that step 3 is handled is that 86 ℃～90 ℃ baking oven is handled 1.8h～2h, promptly obtains the boron nitride ceramics fibre organic precursor method.
The present invention is a feedstock production boron nitride ceramics fibre organic precursor method with trichlorine boron azine and allyl amine, and its composition principle is:
Boron nitride ceramics fibre organic precursor method of the present invention is a raw material with trichlorine boron azine and allyl amine, and reactive polymeric in toluene solvant is removed toluene solvant then again in baking oven earlier; Make the further crosslinking polymerization of precursor, obtaining number-average molecular weight is 2000～2750, the boron nitride ceramics fibre organic precursor method; This precursor is amorphous backbone, under 85 ℃～100 ℃ temperature, gets final product melt-spinning, and is easy to operate; Ropiness is good; The silk that spins is 1000 ℃ of sintering 1 hour in ammonia atmosphere earlier, and then in nitrogen atmosphere 1700 ℃ of sintering 1 hour, promptly obtain SP 1 (h-BN) fiber of pure and well-crystallized's hexagonal structure.The boron nitride fibre that obtains can be used for making advanced refractory materials, TiB
2Spout, high frequency induction furnace liner, thermocouple protective casing and the high-temperature coatings etc. of the rod of the additive of polymkeric substance such as/BN composite ceramics, high temperature lubricant, transistorized heat-sealing siccative, resin, the heatshield material in the aerospace, pile neutron absorption, the structured material of reactor, crucible material, semiconductor packages radiating bottom plate, thrust chamber.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the boron nitride ceramics fibre organic precursor method of embodiment 15 preparations; Fig. 2 is the FFIR figure of the boron nitride ceramics fibre organic precursor method of embodiment 15 preparations; The stereoscan photograph of the boron nitride ceramics fibre organic precursor method silk of Fig. 3 embodiment 15 preparations; Fig. 4 is the stereoscan photograph of the boron nitride ceramics fibre of embodiment 15 preparations; Fig. 5 is the X ray diffracting spectrum of the boron nitride ceramics fibre of embodiment 15 preparations; Fig. 6 is the x-ray photoelectron ability spectrogram of the boron nitride ceramics fibre of embodiment 15 preparations; Fig. 7 is the meticulous spectrogram of x-ray photoelectron power spectrum of B element of the boron nitride ceramics fibre of embodiment 15 preparation; Fig. 8 is the meticulous spectrogram of x-ray photoelectron power spectrum of N element of the boron nitride ceramics fibre of embodiment 15 preparation.
Embodiment
Embodiment one: the structural formula of the boron nitride ceramics fibre organic precursor method of this embodiment for
wherein n be 10～13 integer.
The boron nitride ceramics fibre organic precursor method of this embodiment is a raw material with trichlorine boron azine and allyl amine, and reactive polymeric in toluene solvant is removed toluene solvant then again in baking oven earlier; Make the further crosslinking polymerization of precursor, obtaining number-average molecular weight is 2000～2750, the boron nitride ceramics fibre organic precursor method; This precursor is amorphous backbone; Under 85 ℃～100 ℃ temperature, get final product melt-spinning, easy to operate, ropiness is good; Behind the sintering, promptly obtain SP 1 (h-BN) fiber of pure and well-crystallized's hexagonal structure under the condition of the silk that spins 1700 ℃ of nitrogen treatment after handling 1 hour through 1000 ℃ of ammonias.
Embodiment two: the preparation method of the boron nitride ceramics fibre organic precursor method of this embodiment is according to the following steps at relative humidity≤1% and be filled with in the glove box of nitrogen of purity>=99.9% (volume) of 0.1MPa and carry out: be 1: 0.5～1.5 to join in the toluene in molar ratio with trichlorine boron azine and allyl amine one; At room temperature stir 2h～4h, remove by filter white precipitate then; Filtrating the joining of two, getting step 1 has in the reactor drum of cooling and reflux device, opens and stirs, and is warming up to 60 ℃～90 ℃ and keeps 15h～28h, is cooled to room temperature then, obtains liquid form mixt; Three, will be that underpressure distillation removes toluene under 60 ℃～65 ℃ conditions in temperature through the liquid form mixt that step 2 obtains; Four, will place temperature through the liquid form mixt that step 3 is handled is that 86 ℃～90 ℃ baking oven is handled 1.8h～2h, promptly obtains the boron nitride ceramics fibre organic precursor method.
The structural formula of the boron nitride ceramics fibre organic precursor method of this embodiment preparation does
The boron nitride ceramics fibre organic precursor method of this embodiment is a raw material with trichlorine boron azine and allyl amine, and reactive polymeric in toluene solvant is removed toluene solvant then again in baking oven earlier; Make the further crosslinking polymerization of precursor, obtaining number-average molecular weight is 2000～2750, the boron nitride ceramics fibre organic precursor method; This precursor is amorphous backbone; Under 85 ℃～100 ℃ temperature, get final product melt-spinning, easy to operate, ropiness is good; Behind the sintering, promptly obtain SP 1 (h-BN) fiber of pure and well-crystallized's hexagonal structure under the condition of the silk that spins 1700 ℃ of nitrogen treatment after handling 1 hour through 1000 ℃ of ammonias.
Embodiment three: what this embodiment and embodiment two were different is: the trichlorine boron azine in the step 1 prepares according to the following steps: a, 3 grams～8 analytically pure ammonium chlorides of gram and the analytically pure toluene of 400mL are joined in the reactor drum with cooling and reflux device; B, under protection of nitrogen gas, feed boron trichloride 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; Filtrating underpressure distillation under 40 ℃～60 ℃ conditions after d, the step of learning from else's experience c handle removes toluene, obtains trichlorine boron azine.Other is identical with embodiment two.
Embodiment four: what this embodiment and embodiment two were different is: the trichlorine boron azine in the step 1 prepares according to the following steps: a, 5 analytically pure ammonium chlorides of gram and the analytically pure toluene of 400mL are joined in the reactor drum with cooling and reflux device; B, under protection of nitrogen gas, feed boron trichloride gas, the flow of control boron trichloride gas is opened and is stirred at 0.3L/min, is warming up to 115 ℃ and keeps 10h, obtains liquid-solid mixture; C, remove by filter solid matter in the liquid-solid mixture; Filtrating underpressure distillation under 50 ℃ of conditions after d, the step of learning from else's experience c handle removes toluene, obtains trichlorine boron azine.Other is identical with embodiment two.
Embodiment five: what this embodiment was different with one of embodiment two to four is: the mol ratio of trichlorine boron azine and allyl amine is 1: 0.7～1.3 in the step 1.Other is identical with one of embodiment two to four.
Embodiment six: what this embodiment was different with one of embodiment two to four is: the mol ratio of trichlorine boron azine and allyl amine is 1: 1 in the step 1.Other is identical with one of embodiment two to four.
Embodiment seven: what this embodiment was different with one of embodiment two to six is: the churning time in the step 1 is 2.5h～3.5h.Other is identical with one of embodiment two to six.
Embodiment eight: what this embodiment was different with one of embodiment two to six is: the churning time in the step 1 is 3h.Other is identical with one of embodiment two to six.
Embodiment nine: what this embodiment was different with one of embodiment two to eight is: the temperature in the step 2 rises to 65 ℃～85 ℃, and the hold-time is 17h～26h.Other is identical with one of embodiment two to eight.
Embodiment ten: what this embodiment was different with one of embodiment two to eight is: the temperature in the step 2 rises to 75 ℃, and the hold-time is 20h.Other is identical with one of embodiment two to eight.
Embodiment 11: what this embodiment was different with one of embodiment two to ten is: be underpressure distillation under 61 ℃～64 ℃ the condition in temperature in the step 3.Other is identical with one of embodiment two to ten.
Embodiment 12: what this embodiment was different with one of embodiment two to ten is: be underpressure distillation under 63 ℃ the condition in temperature in the step 3.Other is identical with one of embodiment two to ten.
Embodiment 13: what this embodiment was different with one of embodiment two to 12 is: temperature of oven is to handle 1.85h～1.95h in 87 ℃～89 ℃ the baking oven in the step 4.Other is identical with one of embodiment two to 12.
Embodiment 14: what this embodiment was different with one of embodiment two to 12 is: temperature of oven is to handle 1.9h in 88 ℃ the baking oven in the step 4.Other is identical with one of embodiment two to 12.
Embodiment 15: the preparation method of the boron nitride ceramics fibre organic precursor method of this embodiment by following according to the following steps relative humidity be 0.81% and the purity that is filled with 0.1MPa be to carry out in the glove box of nitrogen of 99.99% (volume): be to join in toluene at 1: 1.2 in molar ratio one, with trichlorine boron azine and allyl amine; At room temperature stir 2.5h, remove by filter white precipitate then; Filtrating the joining of two, getting step 1 has in the reactor drum of cooling and reflux device, opens and stirs, and is warming up to 75 ℃ and keeps 20h, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 65 ℃ of conditions that step 2 obtains; Four, will place temperature through the liquid form mixt that step 3 is handled is that 90 ℃ baking oven is handled 2h, promptly obtains the boron nitride ceramics fibre organic precursor method.
Trichlorine boron azine in the step 1 of this embodiment prepares according to the following steps: a, 6 gram analytically pure ammonium chlorides and the analytically pure toluene of 400mL are joined in the reactor drum with cooling and reflux device; B, under protection of nitrogen gas, feed boron trichloride gas, the flow of control boron trichloride gas is opened and is stirred at 0.2L/min, is warming up to 120 ℃ and keeps 10h, obtains liquid-solid mixture; C, remove by filter solid matter in the liquid-solid mixture; Filtrating underpressure distillation under 55 ℃ of conditions after d, the step of learning from else's experience c handle removes toluene, obtains trichlorine boron azine.
The structural formula of the boron nitride ceramics fibre organic precursor method of this embodiment preparation is:
wherein n is 10～13 integer.
The number-average molecular weight Mn that uses the gel gc to record the boron nitride ceramics fibre organic precursor method of this embodiment preparation is 2072, and matter average molecular weight Mw is 2164, and Mz is 2293, M
Z+1Be 2469, dispersion polymerization is 1.044372.The X ray diffracting spectrum of the boron nitride ceramics fibre organic precursor method of this embodiment preparation is as shown in Figure 1, and as can beappreciated from fig. 1 this precursor is a non-crystalline state; The FFIR figure of the boron nitride ceramics fibre organic precursor method of this embodiment preparation is as shown in Figure 2, can see that from Fig. 2 the boron nitride ceramics fibre organic precursor method is at 3200cm
-1, 30529cm
-1, 990cm
-1, 1410cm
-1, 690cm
-1There are strong absorption peak, wherein 3200cm in the place
-1, 30529cm
-1Absorption peak be the absorption peak of N-H key, 990cm
-1Absorption peak be the absorption peak of B-Cl key; 1410cm
-1Absorption peak be the absorption peak of B-N key, 690cm
-1The absorption peak at place is the absorption peak of B-N key, conforms to the structural formula of boron nitride ceramics fibre organic precursor method.
The boron nitride ceramics fibre organic precursor method ropiness of this embodiment preparation is good; Behind melt-spinning under 90 ℃ the temperature; The ESEM of the boron nitride ceramics fibre organic precursor method silk that obtains is as shown in Figure 3, the smooth surface of boron nitride ceramics fibre organic precursor method silk, and diameter is 40 μ m.
The method for preparing boron nitride ceramics fibre with boron nitride ceramics fibre organic precursor method silk is carried out according to the following steps: a, boron nitride ceramics fibre organic precursor method silk is placed in the sintering oven; Under ammonia atmosphere; Rise to 1000 ℃ and be incubated 1 hour with the temperature rise rate of 2 ℃/min, cool to room temperature then with the furnace; B, the atmosphere of sintering oven is replaced into nitrogen atmosphere, is warming up to 1700 ℃ and be incubated 1 hour, cool to room temperature then with the furnace, obtain boron nitride ceramics fibre with the speed of 10 ℃/min.
The ESEM of the boron nitride ceramics fibre that obtains is as shown in Figure 4; As can beappreciated from fig. 4; The boron nitride ceramics fibre surface smoother that obtains after the cracking of boron nitride ceramics fibre organic precursor method does not have tangible surface imperfection, and diameter is 35 μ m～40 μ m after the cracking; The X ray diffracting spectrum of boron nitride ceramics fibre is as shown in Figure 5, and as can beappreciated from fig. 5, boron nitride ceramics fibre is made up of cubic boron nitride crystal, and the split product crystallization is intact, does not have other dephasigns and produces; The XPS collection of illustrative plates of boron nitride ceramics fibre is as shown in Figure 6; Fig. 7 is the meticulous spectrum of XPS of the B element of boron nitride ceramics fibre; Fig. 8 is the meticulous spectrum of XPS of the N element of boron nitride ceramics fibre; The boron nitride ceramics fibre that as can beappreciated from fig. 6 obtains after the cracking of boron nitride ceramics fibre organic precursor method is purer on chemical constitution, and is mainly elementary composition by N element and B, and C 1s and O1s peak mainly are because the sample CO absorption
2Causing with airborne moisture, according to the calculating of peak area among Fig. 7 and Fig. 8, is B: N=1 to obtain the element ratio: 0.93, meet the stoichiometric ratio of SP 1.
Claims (8)
1. boron nitride ceramics fibre organic precursor method, the structural formula that it is characterized in that the boron nitride ceramics fibre organic precursor method for
wherein n be 10～13 integer.
2. the preparation method of boron nitride ceramics fibre organic precursor method as claimed in claim 1; The preparation method who it is characterized in that the boron nitride ceramics fibre organic precursor method is according to the following steps at relative humidity≤1% and be filled with in the glove box of nitrogen of purity>=99.9% (volume) of 0.1MPa and carry out: be 1: 0.5～1.5 to join in the toluene in molar ratio with trichlorine boron azine and allyl amine one; At room temperature stir 2h～4h, remove by filter white precipitate then; Filtrating the joining of two, getting step 1 has in the reactor drum of cooling and reflux device, opens and stirs, and is warming up to 60 ℃～90 ℃ and keeps 15h～28h, is cooled to room temperature then, obtains liquid form mixt; Three, will remove toluene through liquid form mixt underpressure distillation under 60 ℃～65 ℃ conditions that step 2 obtains; Four, will place temperature through the liquid form mixt that step 3 is handled is that 86 ℃～90 ℃ baking oven is handled 1.8h～2h, promptly obtains the boron nitride ceramics fibre organic precursor method.
3. the preparation method of boron nitride ceramics fibre organic precursor method according to claim 2 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 drum with cooling and reflux device; B, under protection of nitrogen gas, feed boron trichloride 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; Filtrating underpressure distillation under 40 ℃～60 ℃ conditions after d, the step of learning from else's experience c handle removes toluene, obtains trichlorine boron azine.
4. according to the preparation method of claim 2 or 3 described boron nitride ceramics fibre organic precursor methods, it is characterized in that the mol ratio of trichlorine boron azine and allyl amine is 1: 0.7～1.3 in the step 1.
5. according to the preparation method of claim 2 or 3 described boron nitride ceramics fibre organic precursor methods, it is characterized in that the churning time in the step 1 is 2.5h～3.5h.
6. according to the preparation method of claim 2 or 3 described boron nitride ceramics fibre organic precursor methods, it is characterized in that the temperature in the step 2 rises to 65 ℃～85 ℃, the hold-time is 17h～26h.
7. according to the preparation method of claim 2 or 3 described boron nitride ceramics fibre organic precursor methods, it is characterized in that in the step 3 that in temperature be underpressure distillation under 61 ℃～64 ℃ the condition.
8. according to the preparation method of claim 2 or 3 described boron nitride ceramics fibre organic precursor methods, it is characterized in that temperature of oven is 87 ℃～89 ℃ in the step 4, the treatment time is 1.85h～1.95h.
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