CN103333342A - Preparation method for high softening point polyborosilazane - Google Patents
Preparation method for high softening point polyborosilazane Download PDFInfo
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- CN103333342A CN103333342A CN2013103018110A CN201310301811A CN103333342A CN 103333342 A CN103333342 A CN 103333342A CN 2013103018110 A CN2013103018110 A CN 2013103018110A CN 201310301811 A CN201310301811 A CN 201310301811A CN 103333342 A CN103333342 A CN 103333342A
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- boron azine
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Abstract
The invention discloses a preparation method for high softening point polyborosilazane, which comprises the following steps: (1) a reaction still provided with a stirring device, a temperature measurement device, a charging device, a ventilation device, a discharging device, and a distillation device is used for replacement of nitrogen; (2)chlorosilane, dialkyl group borazine and heptamethyldisilazane are weighed according to the molar ratio of 1:(0.5-3):(6-12); (3) chlorosilane, dialkyl group borazine and heptamethyldisilazane are added into the reaction still, and the reaction still is cooled to 5-55 below zero DEG C; the heptamethyldisilazane is added into a reactor at the speed of 0.01-0.2L/min and is stirred; (4) after the charging is completed, the reactor is heated to reach 250-350 DEG C and is distilled for 6-48 hours under the normal pressure; (5) after the distillation under the normal pressure is completed, the temperature of the reactor is reduced by 10-60 DEG C and is subjected to reduced pressure distillation for 0.3-3 hours. The softening point of polyborosilazane is synthesized by the method is greater than 180 DEG C, the ceramic yield is more than 60 percent, and high performance ceramic fiber and ceramic matrix can be prepared.
Description
Technical field
The present invention relates to the preparation method of the poly-borosilicate azane of a kind of high softening-point, especially relate to a kind of preparation method of SiBNC ceramic precursor.
Background technology
The SiBNC pottery has excellent high-temperature oxidation and high-temperature creep resistance, has important application prospects in fields such as Aeronautics and Astronautics, weapons, naval vessels.Because of the material self character, be difficult to by inorganic method synthetic.The precursor conversion method is the most effectively preparation method of this class stupalith.
At present, the preparation method of SiBNC ceramic precursor mainly contains polymkeric substance route and monomer route.
It is Si-B-N-C precursor (Chem.Mater, 2002, the 14:3398 that contains the B group that the polymkeric substance route refers to carry out modification and obtain side group with the polymkeric substance that boron-containing compound contains the Si-N key to polysilazane etc.; Chem.Mater, 1995,7:2203; J.Organomet.Chem, 2003,688:27; J.Non-Cryst.Solids, 2004,348:156; J.Eur.Ceram.Soc, 2002,22:1631).Modification obtains poly-borosilicate azane (Chem.Mater, 1995,7:2203 to the hydrogenation polysilazane with the derivative of borine or borazine as Sneddon etc.; Chem.Mater, 1997,9: 2218).The precursor that obtains by this approach generally has higher molecular weight, reaches the even of molecular level but be difficult to that element is distributed, and like this, the resistance to elevated temperatures of gained pottery is relatively poor.
The monomer route refers to the synthetic monomer that contains Si, B, N, four kinds of elements of C earlier, makes the precursor polymerization of single source by rights, obtains 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 in the ceramic product (
J.Mater.Chem, 2005,15,289; Chem.Mater, 2004,16:418; J.Organomet.Chem, 2002,659:29; J.Eur.Ceram.Soc, 2002,22:1631; Chem.Mater, 2005,17:2340).Be starting raw material as Jansen etc. with hexamethyldisilazane, halosilanes, boron trichloride etc., synthetic at low temperatures single source precursor, (US 5834388 to obtain poly-borosilicate azane by ammonia solution or aminolysis polymerization again; US 5885519; US 5968859; US2004/0019230A1).The precursor structure that this synthetic method obtains is single, but two steps of reaction needed are finished the first step synthon, the monomer party of second step, complicated operation.
Lee etc. have invented the method by the poly-borosilicate azane of approach preparation of small molecules cocondensation, namely adopt boron trichloride, trichlorosilane and hexamethyldisilazane, under 125-300 ℃ condition, heat, can obtain a kind of poly-borosilicate azane (US2005/0026769A1; J.Non-Cryst.Solids, 2005,351:2995).This method technological process is simple relatively, and still, its precursor that obtains is the precursor of highly branched crosslinked shape often, causes the precursor can not fusion and dissolving, is unfavorable for actual use.
It is starting raw material that Tang Yun etc. have invented with halosilanes, boron alkyl halide, small molecules disilazane, after mixing according to a certain ratio, is warming up to 150-500 ℃, can obtain liquid or solid-state poly-borosilicate azane (ZL200710035733.9; ZL200810031252.5; ZL200810031250.6).The processing characteristics of the prepared precursor of this method is better, but institute synthesize gather the borosilicate azane softening temperature less than 160 ℃, ceramic yield is on the low side.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of technology simple, easy and simple to handle, the preparation method of the poly-borosilicate azane of high softening-point that productive rate is high.
The present invention solve that its technical problem adopts technical scheme be: the preparation method of the poly-borosilicate azane of a kind of high softening-point may further comprise the steps:
(1) will have the reactor displacement nitrogen of stirring, thermometric, reinforced, ventilation, discharging and water distilling apparatus;
(2) in chlorosilane: dialkyl group boron azine: the mol ratio of heptamethyldisilazane is that the ratio of 1:0.5-3:6-12 takes by weighing chlorosilane, dialkyl group boron azine, heptamethyldisilazane;
(3) earlier chlorosilane, dialkyl group boron azine are added reactor respectively, and reactor is cooled to subzero 5-55 ℃; Again with heptamethyldisilazane with the 0.01-0.2 liter/minute speed add in the reactor, keep stirring;
(4) behind reinforced the finishing, reactor is heated to 250-350 ℃, and under this temperature air distillation 6-48 hour (preferred 15-30 hour);
(5) after air distillation finishes, temperature of reaction kettle is reduced 10-60 ℃, and under this temperature underpressure distillation 0.3-3 hour, be cooled to room temperature.
Further, in the step (2), the general molecular formula of described chlorosilane is R
2 mR
3 nSiCl
(4-m-n), R wherein
2, R
3=H, methyl, ethyl, propyl group, butyl, vinyl, propenyl, allyl group or phenyl; The chlorosilane of described different substituents can use or mix use separately.
Further, in the step (2), described dialkyl group boron azine is B, B '-dimethyl boron azine or B, and B '-diethyl boron azine, described B, B '-dimethyl boron azine, B, B '-diethyl boron azine can use or mix use separately.
The raw material that the present invention selects for use is easy to get, and technology is simple, and controllability is strong, and batch stability is high, is suitable for producing in batches; The poly-borosilicate azane softening temperature that is synthesized is greater than 180 ℃, and ceramic yield is conducive to prepare high performance ceramic fiber and ceramic matrix greater than 60%.
The poly-borosilicate azane that the present invention makes can be used as ceramic precursor for the preparation of SiBNC or SiBN stupalith, can be for the preparation of ceramic fiber, ceramic bulk material, and ceramic matric composite is particularly suitable for preparing ceramic fiber.
Description of drawings
Fig. 1 is the typical infrared spectrogram of the poly-borosilicate azane of the embodiment of the invention 1 gained;
Fig. 2 is the full spectrogram of XPS of the poly-borosilicate azane of the embodiment of the invention 1 gained;
Fig. 3 is the TG spectrogram of the poly-borosilicate azane of the embodiment of the invention 1 gained.
Embodiment
The invention will be further described below in conjunction with embodiment.
Present embodiment may further comprise the steps:
(1) will have the reactor displacement nitrogen of stirring, thermometric, reinforced, ventilation, discharging and water distilling apparatus;
(2) press trichlorosilane: B, B '-dimethyl boron azine: the mol ratio of heptamethyldisilazane is that the ratio of 1:0.5:6 takes by weighing trichlorosilane, B, B '-dimethyl boron azine, heptamethyldisilazane;
(3) earlier with trichlorosilane, B, B '-dimethyl boron azine adds reactor respectively, and reactor is cooled to subzero 5 ℃; Again the speed of heptamethyldisilazane with 0.01 liter/minute is added in the reactor, keep stirring;
(4) behind reinforced the finishing, reactor is heated to 300 ℃, and air distillation 16 hours under this temperature;
(5) after air distillation finishes, temperature of reaction kettle is reduced by 50 ℃, and underpressure distillation 1 hour (vacuum tightness 0.5kPa) under this temperature, be cooled to room temperature, get the poly-borosilicate azane 95g of high softening-point.
The softening temperature of the poly-borosilicate azane of present embodiment gained high softening-point is 182-195 ℃, can be dissolved in organic solvents such as toluene, dimethylbenzene.Its infrared spectrogram, the full spectrogram of XPS, TG spectrogram are respectively as Fig. 1, Fig. 2, shown in Figure 3.
As shown in Figure 1, contain Si-N, B-N, Si-CH in the precursor PBSZ structure
3, N-CH
3Deng chemical bond.
As shown in Figure 2, the target precursor mainly is made up of Si, B, N, C, H and a spot of O.
As shown in Figure 3,1000 ℃ of ceramic yields of poly-borosilicate azane are greater than 65%.
Embodiment 2
Present embodiment may further comprise the steps:
(1) will have the reactor displacement nitrogen of stirring, thermometric, reinforced, ventilation, discharging and water distilling apparatus;
(2) press trichlorosilane: B, B '-dimethyl boron azine: the mol ratio of heptamethyldisilazane is that the ratio of 1:1:6 takes by weighing trichlorosilane, B, B '-dimethyl boron azine, heptamethyldisilazane;
(3) earlier with trichlorosilane, B, B '-dimethyl boron azine adds in the reactor respectively, and reactor is cooled to subzero-55 ℃; Again the speed of heptamethyldisilazane with 0.05 liter/minute is added in the reactor, keep stirring;
(4) behind reinforced the finishing, reactor is heated to 250 ℃, and air distillation 25 hours under this temperature;
(5) after air distillation finishes, temperature of reaction kettle is reduced by 60 ℃, and underpressure distillation 0.3 hour (vacuum tightness 0.1kPa) under this temperature, be cooled to room temperature, get the poly-borosilicate azane 118g of high softening-point.
The softening temperature of the poly-borosilicate azane of present embodiment gained high softening-point is 191-207 ℃, can be dissolved in organic solvents such as toluene, dimethylbenzene.After testing, contain Si-N, B-N, Si-CH in the precursor PBSZ structure
3, N-CH
3Deng chemical bond; The target precursor mainly is made up of Si, B, N, C, H and a spot of O; The ceramic yield of poly-borosilicate azane is greater than 62%.
Embodiment 3
Present embodiment may further comprise the steps:
(1) will have the reactor displacement nitrogen of stirring, thermometric, reinforced, ventilation, discharging and water distilling apparatus;
(2) press methyl ethylene chlorosilane: B, B '-diethyl boron azine: the mol ratio of heptamethyldisilazane is that the ratio of 1:1.5:8 takes by weighing methyl ethylene chlorosilane, B, B '-diethyl boron azine, heptamethyldisilazane;
(3) earlier with methyl ethylene chlorosilane, B, B '-diethyl boron azine adds reactor respectively, and reactor is cooled to subzero 35 ℃; Again the speed of heptamethyldisilazane with 0.1 liter/minute is added in the reactor, keep stirring;
(4) behind reinforced the finishing, reactor is heated to 300 ℃, and air distillation 8 hours under this temperature;
(5) after air distillation finishes, temperature of reaction kettle is reduced by 45 ℃, carry out underpressure distillation 1 hour (vacuum tightness 2kPa), be cooled to room temperature, get the poly-borosilicate azane 146g of high softening-point.
The softening temperature of the poly-borosilicate azane of present embodiment gained high softening-point is 205-219 ℃, can be dissolved in organic solvents such as toluene, dimethylbenzene.After testing, contain Si-N, B-N, Si-CH in the precursor PBSZ structure
3, N-CH
3Deng chemical bond; The target precursor mainly is made up of Si, B, N, C, H and a spot of O; The ceramic yield of poly-borosilicate azane is greater than 66%.
Embodiment 4
Present embodiment may further comprise the steps:
(1) will have the reactor displacement nitrogen of stirring, thermometric, reinforced, ventilation, discharging and water distilling apparatus;
(2) press dichloro methyl silane: B, B '-dimethyl boron azine: the mol ratio of heptamethyldisilazane is that the ratio of 1:2:8 takes by weighing dichloro methyl silane, B, B '-dimethyl boron azine, heptamethyldisilazane;
(3) earlier with dichloro methyl silane, B, B '-dimethyl boron azine adds reactor respectively, and reactor is cooled to subzero 45 ℃; Again the speed of heptamethyldisilazane with 0.15 liter/minute is added in the reactor, keep stirring;
(4) behind reinforced the finishing, reactor is heated to 350 ℃, and air distillation 28 hours under this temperature;
(5) after air distillation finishes, temperature of reaction kettle is reduced by 10 ℃, and underpressure distillation 1 hour (vacuum tightness 4kPa) under this temperature, be cooled to room temperature, get the poly-borosilicate azane 176g of high softening-point.
The softening temperature of the poly-borosilicate azane of present embodiment gained high softening-point is 211-221 ℃, can be dissolved in organic solvents such as toluene, dimethylbenzene.After testing, contain Si-N, B-N, Si-CH in the precursor PBSZ structure
3, N-CH
3Deng chemical bond; The target precursor mainly is made up of Si, B, N, C, H and a spot of O; The ceramic yield of poly-borosilicate azane is greater than 68%.
Embodiment 5
Present embodiment may further comprise the steps:
(1) will have the reactor displacement nitrogen of stirring, thermometric, reinforced, ventilation, discharging and water distilling apparatus;
(2) press dichlorophenyl silane: B, B '-dimethyl boron azine: B, B '-diethyl boron azine: the mol ratio of heptamethyldisilazane is that the ratio of 1:1:2:12 takes by weighing dichlorophenyl silane, B, B '-dimethyl boron azine, B, B '-diethyl boron azine, heptamethyldisilazane;
(3) earlier with dichlorophenyl silane, B, B '-dimethyl boron azine, B, B '-diethyl boron azine adds reactor respectively, and reactor is cooled to subzero 50 ℃; Again the speed of heptamethyldisilazane with 0.2 liter/minute is added in the reactor, keep stirring;
(4) behind reinforced the finishing, with 320 ℃ of reactor heating, and air distillation 15 hours under this temperature;
(5) after air distillation finishes, temperature of reaction kettle is reduced by 20 ℃, and underpressure distillation 3 hours (vacuum tightness 10kPa) under this temperature, be cooled to room temperature, get the poly-borosilicate azane 125g of high softening-point.
The softening temperature of the poly-borosilicate azane of present embodiment gained high softening-point is 196-208 ℃, can be dissolved in organic solvents such as toluene, dimethylbenzene.After testing, contain Si-N, B-N, Si-CH in the precursor PBSZ structure
3, N-CH
3Deng chemical bond; The target precursor mainly is made up of Si, B, N, C, H and a spot of O; The ceramic yield of poly-borosilicate azane is greater than 65%.
Embodiment 6
Present embodiment may further comprise the steps:
(1) will have the reactor displacement nitrogen of stirring, thermometric, reinforced, ventilation, discharging and water distilling apparatus;
(2) press dichlorosilane: B, B '-dimethyl boron azine: the mol ratio of heptamethyldisilazane is that the ratio of 1:2.5:12 takes by weighing dichlorosilane, B, B '-dimethyl boron azine, heptamethyldisilazane;
(3) earlier with dichlorosilane, B, B '-dimethyl boron azine adds reactor respectively, and reactor is cooled to subzero 55 ℃; Again the speed of heptamethyldisilazane with 0.18 liter/minute is added in the reactor, keep stirring;
(4) behind reinforced the finishing, reactor is heated to 350 ℃, and air distillation 48 hours under this temperature;
(5) after air distillation finishes, temperature of reaction kettle is reduced by 60 ℃, and underpressure distillation 3 hours (vacuum tightness 0.1kPa) under this temperature, be cooled to room temperature, get the poly-borosilicate azane 95g of high softening-point.
The softening temperature of the poly-borosilicate azane of present embodiment gained high softening-point is 192-201 ℃, can be dissolved in organic solvents such as toluene, dimethylbenzene.After testing, contain Si-N, B-N, Si-CH in the precursor PBSZ structure
3, N-CH
3Deng chemical bond; The target precursor mainly is made up of Si, B, N, C, H and a spot of O; The ceramic yield of poly-borosilicate azane is greater than 63%.
Claims (3)
1. the preparation method of the poly-borosilicate azane of high softening-point is characterized in that, may further comprise the steps:
(1) will have the reactor displacement nitrogen of stirring, thermometric, reinforced, ventilation, discharging and water distilling apparatus;
(2) in chlorosilane: dialkyl group boron azine: the mol ratio of heptamethyldisilazane is that the ratio of 1:0.5-3:6-12 takes by weighing chlorosilane, dialkyl group boron azine, heptamethyldisilazane;
(3) earlier chlorosilane, dialkyl group boron azine are added reactor respectively, and reactor is cooled to subzero 5-55 ℃; Again with heptamethyldisilazane with the 0.01-0.2 liter/minute speed add in the reactor, keep stirring;
(4) behind reinforced the finishing, reactor is heated to 250-350 ℃, and under this temperature air distillation 6-48 hour;
(5) after air distillation finishes, temperature of reaction kettle is reduced 10-60 ℃, and under this temperature underpressure distillation 0.3-3 hour, be cooled to room temperature.
2. high softening-point according to claim 1 gathers the preparation method of borosilicate azane, and it is characterized in that: in the step (2), the general molecular formula of described chlorosilane is R
2 mR
3 nSiCl
(4-m-n), R wherein
2, R
3=H, methyl, ethyl, propyl group, butyl, vinyl, propenyl, allyl group or phenyl; The chlorosilane of described different substituents uses separately or mixes and use.
3. high softening-point according to claim 1 gathers the preparation method of borosilicate azane, it is characterized in that: in the step (2), described dialkyl group boron azine is B, B '-dimethyl boron azine or B, B '-diethyl boron azine, described B, B '-dimethyl boron azine, B, B '-diethyl boron azine uses separately or mixes and use.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964856A (en) * | 2014-05-26 | 2014-08-06 | 中国人民解放军国防科学技术大学 | Synthesis method of zirconium boride ceramic precursor |
| CN106835358A (en) * | 2016-12-29 | 2017-06-13 | 东华大学 | A kind of preparation method of the SiBNC precursor fibres of ceramic yield high |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964856A (en) * | 2014-05-26 | 2014-08-06 | 中国人民解放军国防科学技术大学 | Synthesis method of zirconium boride ceramic precursor |
| CN106835358A (en) * | 2016-12-29 | 2017-06-13 | 东华大学 | A kind of preparation method of the SiBNC precursor fibres of ceramic yield high |
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