CN102504269A - Preparation method of polyborosilazane precursor - Google Patents
Preparation method of polyborosilazane precursor Download PDFInfo
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- CN102504269A CN102504269A CN2011103076687A CN201110307668A CN102504269A CN 102504269 A CN102504269 A CN 102504269A CN 2011103076687 A CN2011103076687 A CN 2011103076687A CN 201110307668 A CN201110307668 A CN 201110307668A CN 102504269 A CN102504269 A CN 102504269A
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- boron trichloride
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Abstract
The invention relates to a preparation method of a polyborosilazane precursor, comprising the following steps: dropwise adding and stirring boron trichloride and heptamethyldisilazane which are used as starting raw materials into a reactor, wherein the molar ratio of the boron trichloride to the heptamethyldisilazane is 1:3 to 1:10; increasing the temperature of the reactor to 150-500 DEG C, and preserving the temperature for 10-40 hours; decreasing the temperature of the reactor to room temperature to 300 DEG C, carrying out reduced pressure distillation for 0.1-3 hours, removing solvent and low molecules, and decreasing the temperature of the system to room temperature to obtain the polyborosilazane precursor. The reaction process is simple, the synthesis yield is high, and the cost is low, The prepared polyborosilazane precursor has a wide range of application, can be used for preparing ceramic fibers, ceramic bulk materials and ceramic matrix composite materials is particularly suitable for preparing the wave-transmitting ceramic materials.
Description
Technical field
The present invention relates to a kind of siliceous preparation method who gathers boron azane precursor.
Background technology
The existing preparation method who gathers boron azane precursor mainly can be divided into two kinds according to the difference of initial feed: be initial feed with the boron trichloride and be initial feed with the trichlorine borazine.Wherein initial feed trichlorine borazine generally is to be prepared by boron trichloride, therefore adopt boron trichloride be initial feed directly preparation gather boron azane precursor and have that technology is simple, cost is low, be easy to industrialized advantage.Adopting at present boron trichloride is that initial feed one step preparation gathers the boron azane and mainly adopts boron trichloride and siliceous amine (like hexamethyldisilazane) prepared in reaction and adopt boron trichloride and not siliceous amine (methylamine, n n dimetylaniline, aniline and monomethylaniline) prepared in reaction.Wherein adopt boron trichloride acutely restive with not siliceous amine reaction, product is crosslinked easily in subsequent disposal; And adopting boron trichloride and siliceous amine to react controlled, product structure is controlled.Boron trichloride and siliceous amine reaction one step preparation gather the boron azane at first by employing boron trichloride and hexamethyldisilazane prepared in reaction (Guo Xiusheng etc. such as Chen Chaohui; XI AN JIAOTONG UNIVERSITY Subject Index; 2003; 37 (2)), its reaction process is: at first boron trichloride and triethylamine are formed boron trichloride triethylamine title complex at low temperatures, and carry out the suction filtration purifying; Toluene solution with hexamethyldisilazane and boron trichloride triethylamine title complex reacts then; Also need suction filtration to remove unnecessary boron trichloride triethylamine title complex and triethylamine and toluene after the back flow reaction and obtain intermediate product; At last the intermediate product reflux that obtains is steamed small molecules and obtain the siliceous boron azane that gathers of final product.This reaction process step is more, particularly will the rate of taking out prepare boron trichloride triethylamine title complex, and will in follow-up reaction, remove unnecessary boron trichloride triethylamine title complex by suction filtration, and the efficient of influence preparation has increased the cost for preparing.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of prior art, a kind of siliceous preparation method who gathers the boron azane is provided, simple to realize preparing method's technology, cost is low.
Technical scheme of the present invention is: with boron trichloride and seven methyl disilazanes is starting raw material, after mixing according to a certain ratio, is warming up to 150～500 ℃, the insulation certain hour, and cooling back underpressure distillation is cooled to room temperature and promptly obtains the siliceous boron azane precursor of gathering.
The present invention includes following steps:
(1) boron trichloride is dissolved in the organic solvent, is made into the solution that concentration is 1～4mol/L;
(2) will vacuumize, fill air and the moisture that drying nitrogen is got rid of wherein for 3-5 time repeatedly with the reactor drum of stirring, constant pressure funnel, water distilling apparatus, with extremely subzero 2～35 ℃ of reactor drum precoolings;
(3) with raw material boron trichloride and seven methyl disilazanes by boron trichloride: the mol ratio of seven methyl disilazanes=1: 3～1: 10 adds in the reactor drum stirring while dripping with the mode that drips;
(4) reactor drum slowly is heated to 150～500 ℃, is incubated 10～40 hours;
(5) temperature of reactor is reduced to room temperature～300 ℃, underpressure distillation 0.1～3 hour removes and desolvates, behind the low molecule, system is reduced to room temperature promptly obtain the siliceous boron azane precursor of gathering.
Organic solvent in said (1) step is normal hexane, toluene, YLENE.
The temperature in said (4) step is 300～400 ℃, is incubated 20～30 hours;
Said (5) step cools to 200～300 ℃, underpressure distillation 0.5～2 hour.
The present invention compares with existing method, and following positively effect is arranged: (1) raw materials cost is cheap, from the horse's mouth; (2) do not need triethylamine in the reaction raw materials, in reaction process, reduced processes such as suction filtration, the preparation process is that single step reaction carries out, and reaction process is simple; (3) synthetic yield is high; (4) by product in the reaction is mainly volatile halosilanes, is easy to remove through distillation, need not unnecessary purification operations; And through suitable condition and methylamine reaction, can obtain reactant seven methyl disilazanes, make by product obtain reclaiming, can reduce cost on the one hand, simultaneously advantageous in environment protection and economic aspect.(5) the siliceous boron azane precursor of gathering that makes is elementary composition by Si, B, N, C, H etc.Wherein, Si exists with the Si-C form, and B exists with the BN form, and N is with N-Si, N-B, N-CH
3Form exists; As required, can obtain liquid state, the different precursor of degree of crosslinking such as solid-state, it is of wide application, and can be used to prepare ceramic fiber, ceramic bulk material, and ceramic matric composite is particularly suitable for preparing wave-transmitting ceramic material.
Description of drawings
Fig. 1 is the siliceous infrared spectrogram of gathering boron azane precursor of embodiment 1 gained;
Fig. 2 gathers boron azane precursor for embodiment 1 gained is siliceous
11The B-NMR spectrogram.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1:
(1) get boron trichloride and be dissolved in the normal hexane, the concentration that is made into is the solution of 3.5mol/L;
(2) before synthetic, will have in the there-necked flask reactor drum of 500ml of stirring, water distilling apparatus and constant pressure funnel and vacuumize, fill drying nitrogen repeatedly at least three times, getting rid of air and moisture wherein, and with reactor cooling to subzero 20 ℃;
(3) get in the there-necked flask that boron trichloride hexane solution 50ml is injected into drying nitrogen protection with syringe; Getting seven methyl disilazane 198ml with syringe again is injected in the constant pressure funnel; When stirring, the mode of seven methyl disilazanes with slow dropping is added in the hexane solution of boron trichloride;
(4) dropwise after, slowly be warming up to 350 ℃ with the speed of 0.5 ℃/min, 350 ℃ of insulations 20 hours;
(5) system is cooled to 300 ℃, underpressure distillation 1.5 hours promptly obtains the solid-state siliceous boron azane precursor 12.2g that gathers.Its number-average molecular weight is 1812, and weight-average molecular weight is 3042, and softening temperature is 170-190 ℃, can be dissolved in organic solvents such as chloroform, toluene, and productive rate is 91% of a theoretical yield.
Its infrared spectrogram,
11The B-NMR spectrogram is respectively like Fig. 1, shown in Figure 2.
Precursor is faint yellow transparent solid on macroscopic view, can be known by Fig. 1, contains Si-N, B-N, Si-CH in the precursor PBSZ structure
3, N-CH
3Deng chemical bond.
By Fig. 2 visible, the siliceous boron azane precursor of gathering
11The B-NMR spectrum is unimodal form, and chemical shift δ=29.8 ppm judges that thus the B element has only a kind of structure to exist, and can be judged as BN through the δ value in precursor
3Structure.
Embodiment 2:
(1) getting boron trichloride is dissolved in the toluene; The concentration that is made into is the solution of 1mol/L;
(2) before synthetic, will have in the there-necked flask reactor drum of 250ml of stirring, water distilling apparatus and constant pressure funnel and vacuumize, fill drying nitrogen repeatedly at least three times, getting rid of air and moisture wherein, and with reactor cooling to subzero 5 ℃;
(3) get in the there-necked flask that boron trichloride toluene solution 50ml is injected into drying nitrogen protection with syringe; Getting seven methyl disilazane 98ml with syringe again is injected in the constant pressure funnel; When stirring, the mode of seven methyl disilazanes with slow dropping is added in the toluene solution of boron trichloride;
(4) dropwise after, slowly be warming up to 300 ℃ with the speed of 0.5 ℃/min, 400 ℃ of insulations 10 hours;
(5) system is cooled to 350 ℃, underpressure distillation 0.5 hour promptly obtains the solid-state siliceous boron azane precursor 10.2g that gathers.Its number-average molecular weight is 2682, and weight-average molecular weight is 4630, and softening temperature is 200-215 ℃, can be dissolved in organic solvents such as chloroform, toluene, and productive rate is 86.3% of a theoretical yield.
Embodiment 3:
(1) boron trichloride is dissolved in the YLENE, and the concentration that is made into is the solution of 4mol/L;
(2) before synthetic, will have in the there-necked flask reactor drum of 500ml of stirring, water distilling apparatus and constant pressure funnel and vacuumize, fill drying nitrogen repeatedly at least three times, getting rid of air and moisture wherein, and with reactor cooling to subzero 25 ℃;
(3) get in the there-necked flask that boron trichloride xylene solution 50 ml are injected into drying nitrogen protection with syringe; Getting seven methyl disilazanes, 300 ml with syringe again is injected in the constant pressure funnel; When stirring, the mode of seven methyl disilazanes with slow dropping is added in the xylene solution of boron trichloride;
(4) dropwise after, slowly be warming up to 300 ℃ with the speed of 0.5 ℃/min, 300 ℃ of insulations 30 hours;
(5) system is cooled to 260 ℃, underpressure distillation 1 hour promptly obtains the solid-state siliceous boron azane precursor 8.2g that gathers.Its number-average molecular weight is 1316, and weight-average molecular weight is 1540, and softening temperature is 158-176 ℃, can be dissolved in organic solvents such as chloroform, toluene, and productive rate is 89.8% of a theoretical yield.
Claims (4)
1. a siliceous preparation method who gathers boron azane precursor is characterized in that, may further comprise the steps:
(1) boron trichloride is dissolved in the organic solvent, is made into the solution that concentration is 1～4mol/L;
(2) will vacuumize, fill air and the moisture that drying nitrogen is got rid of wherein for 3-5 time repeatedly with the reactor drum of stirring, constant pressure funnel, water distilling apparatus, with extremely subzero 2～35 ℃ of reactor drum precoolings;
(3) with raw material boron trichloride and seven methyl disilazanes by boron trichloride: the mol ratio of seven methyl disilazanes=1: 3～1: 10 adds in the reactor drum stirring while dripping with the mode that drips;
(4) reactor drum slowly is heated to 150～500 ℃, is incubated 10～40 hours;
(5) temperature of reactor is reduced to room temperature～300 ℃, underpressure distillation 0.1～3 hour removes and desolvates, behind the low molecule, system is reduced to room temperature promptly obtain the siliceous boron azane precursor of gathering.
2. the siliceous preparation method who gathers boron azane precursor according to claim 1 is characterized in that, the organic solvent in said (1) step is normal hexane, toluene, YLENE.
3. the siliceous preparation method who gathers boron azane precursor according to claim 1 is characterized in that, the temperature in said (4) step is 300～400 ℃, is incubated 20～30 hours.
4. the siliceous preparation method who gathers boron azane precursor according to claim 1 is characterized in that, said (5) step cools to 200～300 ℃, underpressure distillation 0.5～2 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103938296A (en) * | 2014-03-18 | 2014-07-23 | 东华大学 | Method for preparation of SiBN(C) ceramic fiber precursor by one-pot technique |
| CN104072785B (en) * | 2014-05-30 | 2017-04-05 | 西北工业大学 | A kind of dissaving polymer and preparation method thereof |
| CN112876258A (en) * | 2021-03-05 | 2021-06-01 | 中国人民解放军国防科技大学 | BCN ceramic precursor containing phenyl and synthesis method thereof |
| CN115260219A (en) * | 2022-07-21 | 2022-11-01 | 中国人民解放军国防科技大学 | Preparation method of non-cyclic linear structure borazane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269969A (en) * | 2008-05-08 | 2008-09-24 | 中国人民解放军国防科学技术大学 | Method for preparing nitride ceramic fibre |
| CN101274941A (en) * | 2008-05-08 | 2008-10-01 | 中国人民解放军国防科学技术大学 | Preparation for polyborosilazanes precursor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269969A (en) * | 2008-05-08 | 2008-09-24 | 中国人民解放军国防科学技术大学 | Method for preparing nitride ceramic fibre |
| CN101274941A (en) * | 2008-05-08 | 2008-10-01 | 中国人民解放军国防科学技术大学 | Preparation for polyborosilazanes precursor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103938296A (en) * | 2014-03-18 | 2014-07-23 | 东华大学 | Method for preparation of SiBN(C) ceramic fiber precursor by one-pot technique |
| CN103938296B (en) * | 2014-03-18 | 2016-09-07 | 东华大学 | A kind of method that one kettle way prepares SiBN (C) ceramic fiber precursor |
| CN104072785B (en) * | 2014-05-30 | 2017-04-05 | 西北工业大学 | A kind of dissaving polymer and preparation method thereof |
| CN112876258A (en) * | 2021-03-05 | 2021-06-01 | 中国人民解放军国防科技大学 | BCN ceramic precursor containing phenyl and synthesis method thereof |
| CN115260219A (en) * | 2022-07-21 | 2022-11-01 | 中国人民解放军国防科技大学 | Preparation method of non-cyclic linear structure borazane |
| CN115260219B (en) * | 2022-07-21 | 2023-09-05 | 中国人民解放军国防科技大学 | Preparation method of borazine with non-loop line structure |
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Application publication date: 20120620 |