CN101274941A - Preparation for polyborosilazanes precursor - Google Patents
Preparation for polyborosilazanes precursor Download PDFInfo
- Publication number
- CN101274941A CN101274941A CNA2008100312506A CN200810031250A CN101274941A CN 101274941 A CN101274941 A CN 101274941A CN A2008100312506 A CNA2008100312506 A CN A2008100312506A CN 200810031250 A CN200810031250 A CN 200810031250A CN 101274941 A CN101274941 A CN 101274941A
- Authority
- CN
- China
- Prior art keywords
- reactor
- halosilanes
- precursor
- alkyl halide
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Ceramic Products (AREA)
Abstract
The invention relates to a preparation method of a polyborosilazane precursor. The preparation method adopts halogenosilane, halogenoborane and small molecular disilazane as initial raw materials which are heated to 150 to 500 DEG C after being mixed according to a certain mixture ratio, kept at the temperature for 2 to 30 hours, decompressed and distilled after the temperature is reduced, and cooled to room temperature, thus the polyborosilazane precursor is prepared. The polyborosilazane precursor prepared by the preparation method can be used for preparing ceramic fibers, ceramic massive material and ceramic-based compound material, and is especially suitable for preparing wave transparent ceramic material.
Description
Technical field
The present invention relates to a kind of polyborosilazanes precursor Preparation Method, especially relate to the polyborosilazanes precursor Preparation Method that a kind of preparation contains the polynary ceramic usefulness of elements such as Si, B, N, C.
Background technology
The polynary pottery that contains elements such as Si, B, N, C has excellent hot strength, high-modulus and excellent high-temperature oxidation and high-temperature creep resistance, therefore, Si-B-N-C system pottery has important application prospects in Aeronautics and Astronautics, weapons, naval vessels etc. need the field of high strength, high-modulus, high temperature resistant, anti-oxidant, heat-shock resistance, high temperature and creep resistance material.
The precursor conversion method is the effective ways of this class stupalith of preparation.At present, the preparation method of Si-B-N-C ceramic precursor mainly contains polymkeric substance route and monomer route.
The polymkeric substance route is meant that the polymkeric substance that polysilazane etc. is contained the Si-N key with boron-containing compound carries out modification and obtains side group is Si-B-N-C precursor (Chem.Mater.2002, the 14:3398 that contains the B group; Chem.Mater., 1993,5:547; Chem.Mater., 1995,7:2203; Chem.Mater., 1997,9:2218; J.Organomet.Chem., 2003,688:27; J.Non-Cryst.Solids, 2004,348:156; J.Organomet.Chem., 2002,659:29; J.Eur.Ceram.Soc., 2000,20:2655; J.Eur.Ceram.Soc., 2001,21:2171; J.Eur.Ceram.Soc., 2002,22:1631).Modification obtains Si-B-N-C ceramic fiber precursor (Chem.Mater., 1993,5:547 to the hydrogenation polysilazane with the derivative of borine or borazine as Sneddon etc.; Chem.Mater., 1995,7:2203; Chem.Mater., 1997,9:2218).Owing to be that polymkeric substance is carried out modification, therefore, the precursor that obtains by this approach generally has higher molecular weight and certain processing characteristics, but be difficult to that element is distributed and reach the even of atom, molecular level, like this, when resulting pottery at high temperature was on active service, easily generation separated and workpiece was lost efficacy.
The monomer route is meant the synthetic earlier monomer that contains Si, B, N, four kinds of elements of C, this monomer often is called as single source precursor (Single Source Precursor), make the precursor polymerization of single source then by rights, obtain the poly-borosilicate azane of Si-B-N-C ceramic precursor.The The Nomenclature Composition and Structure of Complexes feature that the precursor that this approach obtains has often can remain to (Nature, 1996,382:796 in the target ceramic product; Chem.Mater.2000,12:623; J.Mater.Chem., 2005,15,289; Science, 285,30; 699; Chem.Mater., 2004,16:418; J.Organomet.Chem., 2002,659:29; J.Eur.Ceram.Soc., 2002,22:1631; J.Organomet.Chem., 1997,541:345; Chem.Mater.2005,17:2340).Is starting raw material as Jansen etc. with hexamethyldisilazane, halosilanes, boron trichloride etc., at low temperatures through polystep reaction, at first synthetic single source precursor is separated by ammonia again or aminolysis list source precursor makes it polymerization and obtains N-methyl polymerized boron silazane precursor (US 5834388; US5885519; US 5968859; US2004/0019230A1).This synthesis path process very complicated, the cost height is unfavorable for applying.
On this basis, Lee etc. (US 2005/0026769 A1) have invented the method for preparing polymerized boron silazane precursor by the approach of small molecules cocondensation, promptly adopt boron trichloride, trichlorosilane and hexamethyldisilazane, under 125-300 ℃ condition, heat, can obtain a kind of polymerized boron silazane precursor.This method technological process is simple relatively, and still, there is following shortcoming in it, at first, the precursor of the crosslinked shape that its precursor that obtains is highly branched often is difficult to obtain the solvable fusile polymerized boron silazane precursor that can be used for processing, and this has just limited its range of application greatly; Secondly, the precursor activity that this method obtains is higher, simultaneously, and processing condition poor controllability (the US 2005/0026769A1 that this method is used; J.Non-Cryst.Solids., 2005,351:2995).
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of prior art, provide a kind of technology simple, cost is low, the polyborosilazanes precursor Preparation Method that product structure is stable.
The objective of the invention is to be achieved through the following technical solutions: with halosilanes, boron alkyl halide, small molecules disilazane is starting raw material, after mixing according to a certain ratio, be warming up to 150-500 ℃, and under this temperature, be incubated 2-30 hour, cooling back underpressure distillation, be cooled to room temperature, promptly obtain polymerized boron silazane precursor.
Concrete preparation technology comprises the steps:
(1) boron alkyl halide and halosilanes are dissolved in the organic solvent;
(2) will vacuumize repeatedly with the reactor of stirring, constant pressure funnel, water distilling apparatus, fill drying nitrogen at least three times, getting rid of air and moisture wherein, and reactor is chilled to subzero 2-35 ℃ in advance;
(3) raw material boron alkyl halide, halosilanes and small molecules disilazane are pressed the boron alkyl halide: halosilanes: small molecules disilazane=1: 0.1-10: the 3-30 mol ratio, add in the reactor in the mode that drips, stir while dripping;
The molecular formula of described boron alkyl halide is as follows:
BX
aR
1 3-a
Wherein, halogen X=Cl or Br (preferred X=Cl); R
1Organic groups such as=H, methyl, ethyl, propyl group, butyl or phenyl (preferred R
1=H or methyl); A=1,2 or 3 (preferred a=2 or 3); The mixture of the boron alkyl halide that described boron alkyl halide can also be above-mentioned different substituents;
Described halosilanes is an alkyl halogen silanes, and its general molecular formula is:
R
2 mR
3 nSiR
4 (4-m-n)
Alkyl R wherein
2And R
3Organic groups such as=H, methyl, ethyl, propyl group, butyl or phenyl (preferred R
2And R
3=H or methyl); R
2And R
3Can be identical also can be different; Halogen R
4=Cl or Br (preferred R
4=Cl); M and n=0,1,2,3 or 4, m+n＜4 (preferred m+n=0 or 1); Described halosilanes can also be the mixture of the halosilanes of above-mentioned different substituents;
Described small molecules disilazane is the alkyl silyl disilazane, and its general molecular formula is:
(R
5 3Si)
2NR
6
R wherein
5Organic groups such as=H, methyl, ethyl, propyl group, butyl or phenyl (preferred R
5=methyl);
R
6Organic groups such as=methyl, ethyl, propyl group, butyl or phenyl (preferred R
6=methyl);
Described boron alkyl halide, halosilanes and small molecules disilazane add in the reactor in the mode that drips: 1. earlier boron alkyl halide and halosilanes are mixed in the reactor, add the small molecules disilazane by the mode that drips then; Or 2. earlier the small molecules disilazane is added in the reactor, add the mixed solution of boron alkyl halide and halosilanes in reactor by the mode that drips then;
(4) reactor is heated to 150-500 ℃ (preferred 240-350 ℃) after dropwising, and insulation 2-30 hour (preferred 8-16 hour) under this temperature;
(5) temperature of reactor is reduced to room temperature-350 ℃ (preferred 150-300 ℃), under this temperature underpressure distillation 0.2-2 hour (preferred 0.5-1 hour), remove and desolvate, behind the low molecule, system reduced to room temperature can obtain polymerized boron silazane precursor.
The polymerized boron silazane precursor that the present invention makes is elementary composition by Si, B, N, C, H etc., and wherein, Si exists with Si-N, Si-C form, and B exists with the BN form, and N exists with N-Si, N-B, N-C form, and no N-H active group exists.As required, can obtain liquid state, the different precursor of degree of crosslinking such as solid-state, precursor can be used to prepare ceramic fiber, ceramic bulk material, and ceramic matric composite is particularly suitable for preparing wave-transmitting ceramic material.
The raw materials cost that the present invention selects for use is cheap, from the horse's mouth, and reaction process is simple, and higher synthetic yield is arranged; Reduced monomeric reactive behavior, made the reaction conditions window increase, controllability strengthens, and can regulate the performance of precursor in a big way; Reduce the precursor product activity, improved the processing characteristics of precursor thus, enlarged its range of application; In the reaction, by product is mainly volatile halosilanes R
7 3SiR
8(R wherein
7Organic groups such as=H, methyl, ethyl, propyl group, butyl or phenyl, R
8=Cl or Br), be easy to remove by distillation procedure, need not unnecessary purification operations; And, by controlling suitable condition and R
6NH
2Reaction, can obtain reactant (R
5 3Si)
2NR
6, make R
7 3SiR
8Obtain reclaiming, this is advantageous in environment protection and economic aspect.
Description of drawings
Fig. 1 is the typical infrared spectrogram of embodiment 1 gained polymerized boron silazane precursor;
Fig. 2 is the full spectrogram of XPS of embodiment 1 gained polymerized boron silazane precursor;
Fig. 3 is embodiment 1 a gained polymerized boron silazane precursor
11The B-NMR spectrogram;
Fig. 4 is embodiment 1 a gained polymerized boron silazane precursor
29The Si-NMR spectrogram.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) boron trichloride and trichlorosilane dissolving are kept in the normal hexane; (2) will have in the there-necked flask reactor of 250ml of stirring, water distilling apparatus and constant pressure funnel and vacuumize, fill drying nitrogen repeatedly three times, and with reactor cooling to subzero 15 ℃; (3) get trichlorosilane 0.15mol with syringe, boron trichloride 0.15mol successively is injected in the there-necked flask of drying nitrogen protection, getting heptamethyldisilazane 0.9mol with syringe again is injected in the constant pressure funnel, stir on one side, on one side heptamethyldisilazane is added in preceding two kinds of monomeric mixed solutions in the mode that drips; (4) dropwise after, be warming up to 270 ℃ with the speed of 0.5 ℃/min, 270 ℃ of insulations 10 hours; (5) system is cooled to 150 ℃, underpressure distillation 0.5 hour promptly obtains solid-state polymerized boron silazane precursor 12.2g.Its number-average molecular weight is 9812, and weight-average molecular weight is 14042, and softening temperature is 131-140 ℃, can be dissolved in organic solvents such as chloroform, toluene, and productive rate is 91% of a theoretical yield.
Its infrared spectrogram, the full spectrogram of XPS,
11The B-NMR spectrogram,
29The Si-NMR spectrogram is respectively as Fig. 1, Fig. 2, Fig. 3, shown in Figure 4.
As shown in Figure 1, contain Si-N, B-N, Si-CH in the precursor PBSZ structure
3, N-CH
3Deng chemical bond.
As seen from Figure 2, the target precursor mainly is made up of Si, B, N, C, H and a spot of O.
From Fig. 3 as seen, polymerized boron silazane precursor
11The B-NMR spectrum is unimodal form, and chemical shift δ=27.8ppm judges that thus the B element has only a kind of structure to exist, and can be judged as BN by the δ value in precursor
3Structure.
As shown in Figure 4, the Si in the polymerized boron silazane precursor presents complicated structure, and SiC is arranged respectively
3N, HSiN
2C, C
2SiN
2Etc. chemical environment.
(1) methyl dichloro boron and silicon tetrachloride dissolving are kept in the normal hexane; (2) will have in the there-necked flask reactor of 500ml of stirring, water distilling apparatus and constant pressure funnel and vacuumize, fill drying nitrogen repeatedly four times, and with reactor cooling to subzero 10 ℃; (3) get silicon tetrachloride 0.15mol with syringe, methyl dichloro boron 0.3mol successively is injected in the there-necked flask of drying nitrogen protection, getting N-ethyl hexamethyldisilazane 1.5mol with syringe again is injected in the constant pressure funnel, when stirring, N-ethyl hexamethyldisilazane is added in preceding two kinds of monomeric mixed solutions in the mode that drips; (4) dropwise after, be warming up to 300 ℃ with the speed of 0.5 ℃/min, 300 ℃ of insulations 12 hours; (5) system is reduced to 165 ℃, underpressure distillation 0.5 hour promptly obtains solid-state polymerized boron silazane precursor 14.6g.Its number-average molecular weight is 9682, and weight-average molecular weight is 14631, and softening temperature is 141-149 ℃, can be dissolved in organic solvents such as chloroform, toluene, and productive rate is 86.3% of a theoretical yield.
Embodiment 3
(1) phenyl boron dichloride and butyl trichlorosilane dissolving are kept in the normal hexane; (2) before synthetic, will have in the there-necked flask reactor of 250ml of stirring, water distilling apparatus and constant pressure funnel and vacuumize, fill drying nitrogen repeatedly three times, and with reactor cooling to subzero 10 ℃; (3) get butyl trichlorosilane 0.15mol with syringe, phenyl boron dichloride 0.15mol successively is injected in the there-necked flask of drying nitrogen protection, getting N-methyl hexaethyl disilazine 1mol with syringe again is injected in the constant pressure funnel, when stirring, N-methyl hexaethyl disilazine is added in preceding two kinds of monomeric mixed solutions in the mode that drips; (4) dropwise after, be warming up to 320 ℃ with the speed of 0.3 ℃/min, 320 ℃ of insulations 12 hours; (5) system is reduced to 182 ℃, underpressure distillation 1 hour promptly obtains solid-state polymerized boron silazane precursor 10.8g.Its number-average molecular weight is 10316, and weight-average molecular weight is 15404, and softening temperature is 138-152 ℃, can be dissolved in organic solvents such as chloroform, toluene, and productive rate is 89.8% of a theoretical yield.
Embodiment 4
(1) ethyl two chloroboranes and the dissolving of dichloro hydrogen silicon are kept in the normal hexane; (2) before synthetic, will have in the there-necked flask reactor 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 dichloro hydrogen silicon 0.6mol with syringe, ethyl two chloroborane 0.15mol successively are injected in the there-necked flask of drying nitrogen protection, getting N-phenyl hexamethyldisilazane 2mol with syringe again is injected in the constant pressure funnel, when stirring, N-phenyl hexamethyldisilazane is added in preceding two kinds of monomeric mixed solutions in the mode that drips; (4) dropwise after, be warming up to 280 ℃ with the speed of 0.5 ℃/min, 280 ℃ of insulations 8 hours; (5) system is reduced to 140 ℃, underpressure distillation 0.5 hour promptly obtains liquid polymerized boron silazane precursor 28.9g.Its number-average molecular weight is 5812, and weight-average molecular weight is 9042, can be dissolved in organic solvents such as chloroform, toluene, and productive rate is 81.3% of a theoretical yield.
Embodiment 5
(1) boron trichloride and the dissolving of dichloro propyl silane are kept in the normal hexane; (2) will have in the there-necked flask reactor of 250ml of stirring, water distilling apparatus and constant pressure funnel and vacuumize, fill drying nitrogen three times, and with reactor cooling to subzero 15 ℃; (3) get dichloro propyl silane 0.45mol with syringe, boron trichloride 0.15mol successively is injected in the there-necked flask of drying nitrogen protection, getting N-methyl six propyl group disilazane 1.5mol with syringe again is injected in the constant pressure funnel, when stirring, N-methyl six propyl group disilazanes are added in preceding two kinds of monomeric mixed solutions in the mode that drips; (4) dropwise after, be warming up to 250 ℃ with the speed of 0.5 ℃/min, 250 ℃ of insulations 8 hours; (5) system is reduced to 120 ℃, underpressure distillation 0.5 hour promptly obtains liquid polymerized boron silazane precursor 19.2g.Its number-average molecular weight is 5812, and weight-average molecular weight is 9072, can be dissolved in organic solvents such as chloroform, toluene, and productive rate is 80.6% of a theoretical yield.
Embodiment 6
(1) propyl group dichloride boron and diphenyl dichlorosilane dissolving are kept in the normal hexane; (2) will have in the there-necked flask reactor of 250ml of stirring, water distilling apparatus and constant pressure funnel and vacuumize, fill drying nitrogen repeatedly at least three times, and with reactor cooling to subzero 15 ℃; (3) getting heptamethyldisilazane 0.9mol with syringe is added in the there-necked flask, again with diphenyl dichlorosilane 0.15mol, propyl group dichloride boron 0.3mol successively is injected in the constant pressure funnel, when stirring, with the mixing liquid of diphenyl dichlorosilane and propyl group dichloride boron with speed drop in the heptamethyldisilazane; (4) dropwise after, be warming up to 330 ℃ with the speed of 0.5 ℃/min, 330 ℃ of insulations 15 hours; (5) system is reduced to 195 ℃, underpressure distillation 1 hour promptly obtains solid-state polymerized boron silazane precursor 20.8g.Its number-average molecular weight is 10932, and weight-average molecular weight is 16048, and softening temperature is 149-158 ℃, can be dissolved in organic solvents such as chloroform, toluene, and productive rate is 91% of a theoretical yield.
Claims (3)
1, a kind of polyborosilazanes precursor Preparation Method is characterized in that, comprises the steps:
(1) boron alkyl halide and halosilanes are dissolved in the organic solvent;
(2) will vacuumize repeatedly with the reactor of stirring, constant pressure funnel, water distilling apparatus, fill drying nitrogen at least three times, getting rid of air and moisture wherein, and reactor is chilled to subzero 2-35 ℃ in advance;
(3) raw material boron alkyl halide, halosilanes and small molecules disilazane are pressed the boron alkyl halide: halosilanes: small molecules disilazane=1: 0.1-10: the 3-30 mol ratio, add in the reactor in the mode that drips, stir while dripping;
The molecular formula of described boron alkyl halide is as follows:
BX
aR
1 3-a
Wherein, halogen X=Cl or Br; R
1=H, methyl, ethyl, propyl group, butyl or phenyl; A=1,2 or 3; The mixture of the boron alkyl halide that described boron alkyl halide can also be above-mentioned different substituents;
Described halosilanes is an alkyl halogen silanes, and its general molecular formula is:
R
2 mR
3 nSiR
4 (4-m-n)
Alkyl R wherein
2And R
3=H, methyl, ethyl, propyl group, butyl or phenyl; R
2And R
3Can be identical also can be different; Halogen R
4=Cl or Br; M and n=0,1,2,3 or 4, m+n＜4; Described halosilanes can also be the mixture of the halosilanes of above-mentioned different substituents;
Described small molecules disilazane is the alkyl silyl disilazane, and its general molecular formula is:
(R
5 3Si)
2NR
6
R wherein
5=H, methyl, ethyl, propyl group, butyl or phenyl;
R
6=methyl, ethyl, propyl group, butyl or phenyl;
Described boron alkyl halide, halosilanes and small molecules disilazane add in the reactor in the mode that drips: 1. earlier boron alkyl halide and halosilanes are mixed in the reactor, add the small molecules disilazane by the mode that drips then; Or 2. earlier the small molecules disilazane is added in the reactor, add the mixed solution of boron alkyl halide and halosilanes in reactor by the mode that drips then;
(4) reactor is heated to 150-500 ℃ after dropwising, and insulation 2-30 hour under this temperature;
(5) temperature of reactor is reduced to room temperature-350 ℃, under this temperature underpressure distillation 0.2-2 hour, remove and desolvate, behind the low molecule, system reduced to room temperature can obtain polymerized boron silazane precursor.
2, polyborosilazanes precursor Preparation Method according to claim 1 is characterized in that, in described (4) step, after dropwising reactor is heated to 240-350 ℃, and is incubated 8-16 hour under this temperature.
3, polyborosilazanes precursor Preparation Method according to claim 1 and 2 is characterized in that, in described (5) step, temperature of reactor is reduced to 150-300 ℃, under this temperature underpressure distillation 0.5-1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100312506A CN101274941B (en) | 2008-05-08 | 2008-05-08 | Preparation for polyborosilazanes precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100312506A CN101274941B (en) | 2008-05-08 | 2008-05-08 | Preparation for polyborosilazanes precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101274941A true CN101274941A (en) | 2008-10-01 |
| CN101274941B CN101274941B (en) | 2010-07-28 |
Family
ID=39994831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100312506A Expired - Fee Related CN101274941B (en) | 2008-05-08 | 2008-05-08 | Preparation for polyborosilazanes precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101274941B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870585A (en) * | 2010-07-06 | 2010-10-27 | 中国人民解放军国防科学技术大学 | Preparation method of Si-Al-C-N ceramic precursor |
| CN102504269A (en) * | 2011-10-12 | 2012-06-20 | 中国人民解放军国防科学技术大学 | Preparation method of polyborosilazane precursor |
| CN102643101A (en) * | 2012-04-18 | 2012-08-22 | 东华大学 | Preparation method of C/SiBNC composite material |
| CN103333342A (en) * | 2013-07-18 | 2013-10-02 | 中国人民解放军国防科学技术大学 | Preparation method for high softening point polyborosilazane |
| CN103333343A (en) * | 2013-07-18 | 2013-10-02 | 中国人民解放军国防科学技术大学 | Preparation method of poly-zirconium-boron-silazane precursor |
| CN104974352A (en) * | 2015-06-24 | 2015-10-14 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of SiBCN ceramic precursor containing borazine structure |
| CN109369918A (en) * | 2018-10-29 | 2019-02-22 | 航天材料及工艺研究所 | A kind of high boron content Si-B-C-N presoma and preparation method thereof |
| CN109704778A (en) * | 2019-01-21 | 2019-05-03 | 武汉科技大学 | A kind of SiBCN ceramics and preparation method thereof |
| CN110066397A (en) * | 2019-04-25 | 2019-07-30 | 中国人民解放军国防科技大学 | Series-parallel synthesis method of polyborosilazane |
| CN113024819A (en) * | 2021-03-05 | 2021-06-25 | 中国人民解放军国防科技大学 | SiBCN ceramic precursor and synthesis method thereof |
| CN115109257A (en) * | 2022-07-21 | 2022-09-27 | 中国人民解放军国防科技大学 | Synthesis method of high molecular weight linear polyboroazane precursor |
-
2008
- 2008-05-08 CN CN2008100312506A patent/CN101274941B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870585A (en) * | 2010-07-06 | 2010-10-27 | 中国人民解放军国防科学技术大学 | Preparation method of Si-Al-C-N ceramic precursor |
| CN102504269A (en) * | 2011-10-12 | 2012-06-20 | 中国人民解放军国防科学技术大学 | Preparation method of polyborosilazane precursor |
| CN102643101A (en) * | 2012-04-18 | 2012-08-22 | 东华大学 | Preparation method of C/SiBNC composite material |
| CN103333342B (en) * | 2013-07-18 | 2015-10-28 | 中国人民解放军国防科学技术大学 | A kind of preparation method of high softening-point PVDF hollow fiber membrane |
| CN103333343A (en) * | 2013-07-18 | 2013-10-02 | 中国人民解放军国防科学技术大学 | Preparation method of poly-zirconium-boron-silazane precursor |
| CN103333342A (en) * | 2013-07-18 | 2013-10-02 | 中国人民解放军国防科学技术大学 | Preparation method for high softening point polyborosilazane |
| CN104974352A (en) * | 2015-06-24 | 2015-10-14 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of SiBCN ceramic precursor containing borazine structure |
| CN109369918A (en) * | 2018-10-29 | 2019-02-22 | 航天材料及工艺研究所 | A kind of high boron content Si-B-C-N presoma and preparation method thereof |
| CN109704778A (en) * | 2019-01-21 | 2019-05-03 | 武汉科技大学 | A kind of SiBCN ceramics and preparation method thereof |
| CN110066397A (en) * | 2019-04-25 | 2019-07-30 | 中国人民解放军国防科技大学 | Series-parallel synthesis method of polyborosilazane |
| CN110066397B (en) * | 2019-04-25 | 2021-03-26 | 中国人民解放军国防科技大学 | Series-parallel synthesis method of polyborosilazane |
| CN113024819A (en) * | 2021-03-05 | 2021-06-25 | 中国人民解放军国防科技大学 | SiBCN ceramic precursor and synthesis method thereof |
| CN115109257A (en) * | 2022-07-21 | 2022-09-27 | 中国人民解放军国防科技大学 | Synthesis method of high molecular weight linear polyboroazane precursor |
| CN115109257B (en) * | 2022-07-21 | 2023-05-09 | 中国人民解放军国防科技大学 | Synthesis method of high molecular weight linear polyborosilazane precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101274941B (en) | 2010-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101274941B (en) | Preparation for polyborosilazanes precursor | |
| CN101269965B (en) | Method for preparing SiBN(C) ceramic fibre | |
| CN102167832B (en) | Poly(carborane-siloxane/silazane) polymer and preparation method thereof | |
| KR840001536B1 (en) | Method of producing for polysilane | |
| CN100491287C (en) | Method for preparing pyro-ceramic fibre | |
| US8466076B2 (en) | Polysilane-polycarbosilanes with reduced chlorine content based on methylchloropolysilanes, and spinning dopes and ceramic moldings produced therefrom | |
| CN105694049B (en) | PVDF hollow fiber membrane and preparation method thereof | |
| CN100591643C (en) | Method for preparing nitride ceramic fibre | |
| CN103214675B (en) | Poly(methylsilane-carbosilane) and preparation method thereof | |
| CN104744706B (en) | The synthetic method of high ceramic yield Polycarbosilane | |
| CN109369918A (en) | A kind of high boron content Si-B-C-N presoma and preparation method thereof | |
| CN104591741B (en) | A kind of preparation method of SiNCB ceramic material | |
| CN102249684A (en) | Preparation method of SiBN(C) ceramic fiber | |
| CN103333341A (en) | High-temperature-resistant hybrid silazane resin and preparation method thereof | |
| CN104130417A (en) | High-temperature silicon alkyne resin containing nitrogen and preparation method thereof | |
| CN100486929C (en) | Method for preparing polymerized boron silazane precursor | |
| CN105542172A (en) | Boron-silicon-alkyne polymer containing carborane in main chain and preparation method of boron-silicon-alkyne polymer | |
| CN102439070B (en) | Reactive inorganic clusters | |
| CN101544765B (en) | Novel high temperature-resisting phenylboronic acid-silane-ethynyl polymer and preparation method thereof | |
| CN101269968B (en) | Method for preparing multicomponent nitride ceramic precursor | |
| CN115651414B (en) | Preparation method of liquid complex-phase SiBCN ceramic precursor and SiBCN ceramic | |
| CN115216016B (en) | Solid polysilazane and preparation method and application thereof | |
| WO2015098738A1 (en) | Polyalkoxysilazane and method for producing same, and coating composition and silicon-based ceramic coating obtained therefrom | |
| CN103333342B (en) | A kind of preparation method of high softening-point PVDF hollow fiber membrane | |
| CN101709062A (en) | Novel silazane-diacetylene aniline silane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100728 Termination date: 20150508 |
|
| EXPY | Termination of patent right or utility model |