CN100579936C - A kind of preparation method of ceramic fiber precursor - Google Patents
A kind of preparation method of ceramic fiber precursor Download PDFInfo
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- CN100579936C CN100579936C CN200710048052A CN200710048052A CN100579936C CN 100579936 C CN100579936 C CN 100579936C CN 200710048052 A CN200710048052 A CN 200710048052A CN 200710048052 A CN200710048052 A CN 200710048052A CN 100579936 C CN100579936 C CN 100579936C
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- 239000002243 precursor Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000835 fiber Substances 0.000 title claims abstract description 23
- 239000000919 ceramic Substances 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- -1 aliphatic secondary amine Chemical class 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000003760 magnetic stirring Methods 0.000 claims abstract 6
- 239000002244 precipitate Substances 0.000 claims abstract 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- DWGWCWDDNTVOGF-UHFFFAOYSA-N Cl.Cl.Cl.Cl.Cl.Cl Chemical compound Cl.Cl.Cl.Cl.Cl.Cl DWGWCWDDNTVOGF-UHFFFAOYSA-N 0.000 claims 1
- 150000003139 primary aliphatic amines Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 8
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 9
- 229910052582 BN Inorganic materials 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- 150000003384 small molecules Chemical class 0.000 description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- 239000006210 lotion Substances 0.000 description 6
- 229910000474 mercury oxide Inorganic materials 0.000 description 6
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 6
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 6
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 229910000062 azane Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- Ceramic Products (AREA)
Abstract
本发明涉及一种陶瓷纤维先驱体的制备方法，步骤包括：(1)小分子单体的制备：在-80℃～0℃、无氧、干燥的氛围下，将与脂肪族仲胺摩尔比为1∶0.2～1∶5的三氯化硼缓慢冷凝到脂肪族仲胺的三乙胺溶液中，磁力搅拌下反应1～20h，再升至室温反应1～20h，产生黄色沉淀，过滤；然后将与脂肪族伯胺摩尔比为1∶1～5∶1的无水甲苯溶液逐滴加入到上述滤液中，伴随磁力搅拌-80℃～0℃下反应1～20h，再升至室温反应5～30h，又产生黄色沉淀，过滤，减压蒸馏；(2)BN先驱体的制备：将上述淡黄色液体在磁力搅拌下进行多阶段线性升温，升温速度为0.5～20℃/min，加热至150℃～180℃，15～25h，冷却后得黄色固体状先驱体。该方法工艺简单，易于实现工业化连续生产。
The present invention relates to a preparation method of a ceramic fiber precursor. The steps include: (1) preparation of a small molecular monomer: at -80°C to 0°C, in an oxygen-free, dry atmosphere, the molar ratio of the aliphatic secondary amine Slowly condense boron trichloride in the ratio of 1:0.2 to 1:5 into the triethylamine solution of aliphatic secondary amines, react under magnetic stirring for 1 to 20 hours, then rise to room temperature and react for 1 to 20 hours to produce a yellow precipitate and filter; Then add the anhydrous toluene solution with a molar ratio of 1:1 to 5:1 to the aliphatic primary amine dropwise into the above filtrate, and react with magnetic stirring at -80°C to 0°C for 1 to 20 hours, then rise to room temperature for reaction 5-30h, a yellow precipitate was produced again, filtered, and distilled under reduced pressure; (2) Preparation of BN precursor: the above-mentioned light yellow liquid was subjected to multi-stage linear heating under magnetic stirring, and the heating rate was 0.5-20°C/min. To 150 ℃ ~ 180 ℃, 15 ~ 25h, after cooling to obtain a yellow solid precursor. The method has simple process and is easy to realize industrialized continuous production.
Description
Technical field
The invention belongs to macromolecule material preparation area, particularly relate to a kind of preparation method of ceramic fiber precursor.
Background technology
The research and development high-performance fiber is the high-performance inorganic ceramic fiber especially, has become one of emphasis of current Materials science research in the world.The BN fiber has had both multiple premium properties, has good compound consistency with resin, metal, pottery.Boron nitride (BN) has the character of many uniquenesses, it has that the electromagnetic radiation resistant of wide region, density are little, high-temperature oxidation resistance, high heat of gasification and excellent lubrication characteristic, compare with graphite, the BN thermal expansivity is little, and can make oxide ceramics have good unreactiveness, can be used as the ideal boundary material, and the BN fiber is expected to have high Young's modulus and has high intensity simultaneously, has been subjected to the extensive concern of material circle as a kind of high performance strongthener.
Because inorganic method has demonstrated many shortcomings that are difficult to overcome on preparation BN fiber, from the end of the eighties abroad to utilizing organic boron-nitrogen polymer to make the BN fiber through spinning, non-melt processed, high-temperature heat treatment for precursor, carried out comparatively extensive studies.The earliest with the organic precursor body method prepare the BN fiber be Japanese scholar Taniguchi in Japan:KoKai 76-53000, report utilize the amino borazole of N-phenyl-B-as precursor pyrolysis prepare tensile strength BN fiber preferably, but regrettably the result of this report can not repeat, and mainly is the existing problems that remove because of carbon.After more than 10 year, Wade has prepared solvable fusile BN precursor, but claims that this precursor melt-spun is a fiber.In recent ten years, the foreign scholar has explored the approach of various preparation BN precursor, B.Bonnetot. at Met.Chem.1994,17,583～593 have reported the novel process for preparing the BN fiber with boron trichloride and the synthetic precursor of methylamine, but this method synthetic precursor is a network-like structure, and viscosity is bigger, is unfavorable for the spinning technique in later stage.This patent is with BCl
3, secondary aliphatic amine and Armeen be raw material, aims to provide a kind of synthetic more novel methods based on poly-boron azane precursor linear structure, that have better spinning property.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of ceramic fiber precursor, the boron nitride ceramics fibre precursor of preparation has more linear structure, good spinning property, help the preparation of boron nitride fibre, can make final boron nitrogen fiber have good wave, this method technology is simple, is easy to realize the industrialization continuous production.
The preparation method of a kind of ceramic fiber precursor provided by the invention, reaction process is as follows:
BCl
3+NHR
1R
2→R
1R
2NBCl
2+HCl ......(1)
R
1R
2NBCl
2+R
3NH
2→(R
1R
2N)B(NHR
3)
2+2HCl ......(2)
The preparation method of a kind of new ceramics fiber precursor provided by the invention comprises the following steps:
(1) preparation of small molecule monomer: under-80 ℃～0 ℃, anaerobic, exsiccant atmosphere, to be that the boron trichloride of (1: 0.2)～(1: 5) slowly condenses in the triethylamine solution of secondary aliphatic amine with the secondary aliphatic amine mol ratio, react 1～20h under the magnetic agitation, rise to room temperature reaction 1～20h again, produce yellow mercury oxide, filter, obtain filtrate; Be that the solution that (1: 1)～(5: 1) are formed dropwise joins in the above-mentioned filtrate with dry toluene and Armeen mol ratio then, follow magnetic agitation-80 ℃～0 ℃ reaction 1～20h down, rise to room temperature reaction 5～30h again, produce yellow mercury oxide again, filter, with the distillation of gained filtrate decompression, get weak yellow liquid shape small molecule monomer;
(2) preparation of BN precursor: above-mentioned weak yellow liquid is carried out the multistage linear temperature increase under magnetic agitation, heat-up rate is 0.5～20 ℃/min, is heated to 150 ℃～180 ℃, and 15～25h gets yellow solid shape precursor after the cooling.Secondary aliphatic amine in the described step (1) is CH
3NHCH
3, CH
3CH
2NHCH
3Or CH
3CH
2NHCH
2CH
3
Armeen in the described step (1) is CH
3NH
2, CH
3CH
2NH
2, CH
3CH
2CH
2NH
2Or CH
3CH
2CH
2CH
2NH
2In a kind of.
The triethylamine solution of the secondary aliphatic amine in the described step (1), the volume ratio of secondary aliphatic amine and triethylamine are (1: 0.5)～(1: 5).
The anhydrous toluene solution of the Armeen in the described step (1), the volume ratio of Armeen and dry toluene are (1: 0.5)～(1: 5).
Filter operation in the described step (1) is carried out under nitrogen or argon shield.
Multistage linear temperature increase in the described step (2) divides 4 stages to finish, and the fs is certain temperature between 50 ℃～100 ℃, and constant temperature keeps 10～60min; Subordinate phase is certain temperature between 100 ℃～150 ℃, and constant temperature keeps 10～60min; Phase III is certain temperature between 150 ℃～160 ℃, and constant temperature keeps 5～20h; The quadravalence section is certain temperature between 160 ℃～200 ℃, and constant temperature keeps 1～5h.
The structure of the yellow solid shape precursor molecule in the described step (2) is based on linear structure.
Described step (1), (2) all are to operate under the atmosphere of anhydrous, anaerobic.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of boron nitride precursor body;
Fig. 2 is the infrared spectrum of boron nitride precursor body;
Fig. 3 is the DSC heating curve of boron nitride precursor body.
Embodiment
The invention will be further elaborated below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in to 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 equivalences fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) preparation of small molecule monomer: get the triethylamine solution that concentration is the 7.55mol/l dimethylamine (volume ratio 1: 1) 26.5ml (0.2mol) in the single port flask of 250ml, flask is moved to PSL-1800 type magnetic agitation cryostat,, temperature-80 ℃ goes out the air of flask the inside with nitrogen replacement; Condense to the reaction vessel from steel cylinder by the boron trichloride of tetrafluoroethylene pipe 23.4g (0.2mol); After the condensation, follow magnetic agitation, reaction 5h; Rise to stirring at room 1h again, produce yellow mercury oxide; Under nitrogen protection, filter, with the washing precipitation of 50ml dry toluene for several times, merge washing lotion and filtrate; Filtrate and washing lotion are moved in the 250ml exsiccant single port flask, and still placing temperature is-80 ℃ cryostat,, and anhydrous toluene solution (volume ratio is 1: the 1) 80ml of methylamine is moved in the 250ml constant pressure funnel, slowly is added drop-wise in the flask magnetic agitation; Reaction 5h rises to room temperature reaction 20h again, produces yellow mercury oxide; Nitrogen protection is filtered down, with the washing precipitation of 50ml dry toluene, merging filtrate and washing lotion; Liquid is placed 500ml single port flask, and underpressure distillation removes and desolvates, and gets weak yellow liquid shape small molecule monomer.
(2) preparation of BN precursor: the weak yellow liquid shape small molecule monomer that obtains in the oil bath heating above-mentioned steps (1), will heat the ammonia that generates with nitrogen gas stream and take out of, and absorb ammonia with acid solution; Temperature rise rate with 5 ℃/min divides four sections heating: room temperature rises to 80 ℃, keeps 30min; Continue to rise to 120 ℃, keep 1h; Rise to 150 ℃ again, keep 15h; Rise to 160 ℃ at last, keep 2h; Along with the carrying out of heating, liquid viscosity becomes greatly gradually, and heating finishes and is the boron nitride precursor body through cooled yellow solid.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of present embodiment institute synthetic boron nitride precursor body, and Fig. 2 is its infrared spectrum, and Fig. 3 is its DSC heating curve.
Embodiment 2
(1) preparation of small molecule monomer: the triethylamine solution 30ml (0.15mol) that gets concentration and be the 5mol/l diethylamine is in the single port flask of 250ml, flask is moved to PSL-1800 type magnetic agitation cryostat,, temperature-80 ℃ goes out the air of flask the inside with argon replaces; Condense to the reaction vessel from steel cylinder by the boron trichloride of tetrafluoroethylene pipe 17.55g (0.15mol); After the condensation, follow magnetic agitation, reaction 10h; Rise to stirring at room 4h again, produce yellow mercury oxide; Under argon shield, filter, with the washing precipitation of 50ml normal hexane for several times, merge washing lotion and filtrate; Filtrate and washing lotion are moved in the 250ml exsiccant single port flask, and still placing temperature is-80 ℃ cryostat,, and hexane solution (volume ratio is 1: the 1) 80ml of methylamine is moved in the 250ml constant pressure funnel, slowly is added drop-wise in the flask magnetic agitation; Reaction 5h rises to room temperature reaction 15h again, produces yellow mercury oxide; Argon shield is filtered down, with the washing precipitation of 50ml normal hexane, merging filtrate and washing lotion; Liquid is placed 500ml single port flask, and underpressure distillation removes and desolvates, and gets weak yellow liquid shape small molecule monomer.
(2) preparation of BN precursor: the weak yellow liquid shape small molecule monomer that obtains in the oil bath heating above-mentioned steps (1), will heat the ammonia that generates with argon gas stream and take out of, and absorb ammonia with acid solution; Temperature rise rate with 5 ℃/min divides four sections heating: room temperature rises to 60 ℃, keeps 1h; Continue to rise to 110 ℃, keep 2h; Rise to 140 ℃ again, keep 12h; Rise to 150 ℃ at last, keep 1h; Along with the carrying out of heating, liquid viscosity becomes greatly gradually, and heating finishes and is the boron nitride precursor body through cooled yellow solid.
Claims (4)
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|---|---|---|---|
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2602280A1 (en) * | 2011-12-09 | 2013-06-12 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | One-pot synthesis of SiBNC preceramic polymer |
| CN114715861B (en) * | 2022-03-24 | 2023-07-28 | 中国人民解放军国防科技大学 | A kind of synthetic method of linear polymer BN precursor |
| CN115109257B (en) * | 2022-07-21 | 2023-05-09 | 中国人民解放军国防科技大学 | A kind of synthetic method of high molecular weight linear polyborazane precursor |
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