CN109438712B - Boron modified polycarbosilane resin and preparation method thereof - Google Patents
Boron modified polycarbosilane resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of boron modified polycarbosilane, belonging to the technical field of novel ceramic material preparation. The reaction raw materials of the invention are common chemical raw materials; the unit price of the raw materials is low, and the preparation process is simple; the novel SiBC ceramic precursor prepared by the invention is low-viscosity liquid at normal temperature, has the viscosity of 10-500mPa.S, and has very good process performance; the novel SiBC ceramic precursor prepared by the invention contains active groups such as Si-H, B-H, C ═ C and the like and unsaturated bonds, can be cured by self-crosslinking, has small curing heat release, low curing weight loss and high ceramic yield at high temperature, and can reach 60-70%; the content proportion of each element of the novel SiBC ceramic precursor prepared by the invention can be adjusted by the feed ratio; the novel SiBC ceramic precursor prepared by the invention can be used for impregnating a matrix of an ultrahigh-temperature ceramic matrix composite material, can also be used for preparing high-performance materials such as ceramic coatings, fibers and the like, and has wide application.
Description
Technical Field
The invention relates to a preparation method of boron modified polycarbosilane, belonging to the technical field of novel ceramic material preparation.
Background
The carbon fiber reinforced silicon carbide ceramic-based composite material is a thermostructural material with high temperature resistance, low density and high toughness. The high-modulus high-temperature-resistant high-density material has excellent performances such as high modulus, high temperature resistance, corrosion resistance, oxidation resistance and low density, and has wide application in high-technology fields such as advanced aerospace vehicle structural components, high-temperature engines, turbines, nuclear reactor walls, high-temperature sensors and the like. In recent years, great technical breakthroughs are continuously made in the aspects of developing carbon fiber reinforced silicon carbide ceramic matrix composite materials and parts, and the leap-over development from small-size blocks to large-size thin walls is realized. But still has the problems of higher cost, mechanical property, oxidation resistance and the like which are still to be optimized. Accordingly, cost reduction and high performance are important directions for the development of next-generation composite materials. The heterogeneous element boron is introduced into the carbon fiber reinforced silicon carbide ceramic matrix composite material, so that the high-temperature mechanical property and the oxidation resistance of the carbon fiber reinforced silicon carbide ceramic matrix composite material can be improved, but in the prior art, methods of introducing boron powder or boron-containing sol and the like are adopted, so that the defects of non-uniform distribution of boron elements in a matrix, low introduction efficiency and the like exist.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art and provides boron modified polycarbosilane resin and a preparation method thereof.
A boron-modified polycarbosilane resin, the structural formula of which is:
wherein:
r: unsaturated groups such as alkynyl, propargyl, and allyl;
n is a positive integer, and n is more than or equal to 1.
A preparation method of boron modified polycarbosilane resin comprises the following steps:
adding an organic solvent into the boron resin, and then stirring at the temperature of 20-140 ℃ until the boron resin is completely dissolved to obtain a transparent solution; adding low-molecular-weight liquid polycarbosilane into the obtained transparent solution, heating and stirring for reaction, wherein the reaction temperature is 50-120 ℃, and the reaction time is 1-100 h; and after the reaction is finished, cooling to room temperature, then rotationally evaporating the organic solvent to obtain a yellow brown transparent liquid resin, namely the novel boron modified polycarbosilane resin, and solidifying and pyrolyzing the resin to obtain the Si/B/C amorphous ceramic.
The preparation reaction formula of the boron modified polycarbosilane resin is as follows:
the curing treatment mode adopts a tube furnace, and the curing system is as follows: keeping the temperature at 100 ℃ for 2h, 150 ℃ for 2h and 180 ℃ for 4h, wherein the heating rate is 1-5 ℃/min, and the curing atmosphere is inert (for example, N2Ar) atmosphere;
the pyrolysis process comprises the following steps: heating to 1300-1500 ℃ at a heating rate of 5-10 ℃/min under an inert atmosphere, and preserving heat for 0.5-10 h;
the organic solvent is toluene, xylene, n-hexane or tetrahydrofuran;
the mass ratio of the boron resin to the organic solvent is as follows: 1: 2-10;
the mass ratio of the boron resin to the low molecular weight liquid polycarbosilane is as follows: 1: 0.5-10;
the preparation method of the low molecular weight liquid polycarbosilane comprises the following steps:
(1) adding magnesium chips into a tetrahydrofuran solvent which is purified and dried to obtain a mixed system;
(2) mixing tetrahydrofuran, unsaturated chloroalkane and chlorosilane monomers to obtain a mixed solution;
(3) dropwise adding the mixed solution obtained in the step (2) into the mixed system obtained in the step (1), stirring for 5-30 hours at the reaction temperature of-30-60 ℃ to obtain a reaction primary product;
(4) and (3) adding petroleum ether, deionized water and concentrated hydrochloric acid into the reaction primary product obtained in the step (3), controlling the reaction temperature to be-20-15 ℃, fully stirring for 0.5-5 hours, standing for 0.5-20 hours, carrying out phase separation, taking the upper organic phase, drying and carrying out rotary evaporation to obtain the low-molecular-weight liquid polycarbosilane.
In the step (1), the mass ratio of the magnesium chips to the tetrahydrofuran is 1: 1-2;
in the step (2), the chlorosilane monomer is chloromethyl dichlorosilane or chloromethyl trichlorosilane; the unsaturated chloroalkane is ethynyl chloride, propargyl chloride or allyl chloride; the mass ratio of the chlorosilane monomer to the tetrahydrofuran is 1: 2-10; the mass ratio of the unsaturated chloroalkane to the chlorosilane monomer is 1: 10-20;
in the step (3), when the mixed solution is dripped into a mixed system, the mass ratio of the magnesium chips to the chlorosilane monomers is 1: 5-10;
in the step (4), petroleum ether, deionized water and concentrated hydrochloric acid are added in a volume ratio of 1: 1-10: 0.1;
in the step (4), the volume sum of the petroleum ether, the deionized water and the concentrated hydrochloric acid added and the volume ratio of the initial reaction product is 1-2: 1;
the preparation method of the boron resin comprises the following steps:
(1) adding boron trichloride gas into purified and dried n-hexane to obtain a solution;
(2) adding methyl vinyl chlorosilane monomers into the solution obtained in the step (1), introducing ammonia gas, stirring for 10-30 hours at the reaction temperature of-10-30 ℃, performing filter pressing on the obtained solution through a filter press, and performing rotary evaporation on the filter-pressed solution to obtain the boron resin.
In the step (1), the mass ratio of the boron trichloride gas to the n-hexane is 1: 5-8;
in the step (2), the mass ratio of the methyl vinyl chlorosilane monomer to the boron trichloride is 1: 0.5-4;
in the step (2), the mass ratio of the boron trichloride to the introduced ammonia gas is 1: 5-8.
The invention has the following advantages:
(1) the reaction raw materials of the invention are common chemical raw materials; the unit price of the raw materials is low, and the preparation process is simple;
(2) the novel SiBC ceramic precursor prepared by the invention is low-viscosity liquid at normal temperature, has the viscosity of 10-500mPa.S, and has very good process performance;
(3) the novel SiBC ceramic precursor prepared by the invention contains active groups such as Si-H, B-H, C ═ C and the like and unsaturated bonds, can be cured by self-crosslinking, has small curing heat release, low curing weight loss and high ceramic yield at high temperature, and can reach 60-70%;
(4) the content proportion of each element of the novel SiBC ceramic precursor prepared by the invention can be adjusted by the feed ratio;
(5) the novel SiBC ceramic precursor prepared by the invention can be used for impregnating a matrix of an ultrahigh-temperature ceramic matrix composite material, can also be used for preparing high-performance materials such as ceramic coatings, fibers and the like, and has wide application.
Drawings
FIG. 1 is a gel permeation chromatogram of a SiBC ceramic precursor prepared in example 1 of the present invention;
FIG. 2 is a thermogravimetric plot of a SiBC ceramic precursor prepared in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the invention carries out characterization research on the related performance of the prepared SiBC ceramic precursor, and adopts a rotor viscometer to characterize the rheological performance of the precursor: viscosity test the viscosity characteristics of the precursor were tested using a Broodfield rotational viscometer with a number 31 spindle at 100rpm with a torque of 50%.
The invention adopts a thermogravimetric analysis instrument to characterize the heat resistance of the SiBC ceramic precursor. And in a nitrogen atmosphere, heating to 900 ℃ at a heating rate of 10 ℃/min, and testing the residual weight to represent the heat resistance of the SiBC ceramic precursor.
Example 1
A500 ml three-necked flask was equipped with a gas introduction piston, a sealing plug, a constant pressure dropping funnel, a condenser tube, a magnetic stirrer and a heating circulation system. All the operation processes are carried out according to Schlenk technology, and a water-free and oxygen-free system is built. 50g of boron resin was added under a flowing atmosphere, then 100g of n-hexane was added with a syringe, and the temperature was raised to 40 ℃ with stirring until the dissolution was complete. Then 100g of liquid polycarbosilane with low molecular weight and containing vinyl is added, the temperature is raised to 50 ℃, the stirring reaction is continued for 10 hours, then the stirring is stopped, the oil bath is removed, and the mixture is kept stand for 10 to 20 hours. And (4) pumping out the solvent to obtain a yellow transparent oily SiBC ceramic precursor. The synthesis yield was 80.30%. The gel permeation chromatogram of the obtained SiBC ceramic precursor is shown in figure 1, and the thermogravimetric spectrum is shown in figure 2;
the reaction formula is as follows:
TGA indicates that the precursor is in N2The residual weight at 900 ℃ was 70.46%, and the viscosity test surface product viscosity was 413mPa.S, as shown in FIG. 2.
Gel permeation chromatography tests show that the molecular weight of the obtained polycarbosilane is as follows: mn is 752 and Mw is 2290.
Example 2
A500 ml three-necked flask was equipped with a gas introduction piston, a sealing plug, a constant pressure dropping funnel, a condenser tube, a magnetic stirrer and a heating circulation system. All the operation processes are carried out according to Schlenk technology, and a water-free and oxygen-free system is built. 100g of boron resin was added under a flowing atmosphere, then 500g of xylene was added by syringe, and the temperature was raised to 50 ℃ with stirring until the dissolution was complete. Then adding 300g of liquid polycarbosilane with low molecular weight and containing allyl, heating to 90 ℃, continuing stirring for reaction for 10 hours, then stopping stirring, removing the oil bath, and standing for 10-20 hours. And (4) pumping out the solvent to obtain a yellow transparent oily SiBC ceramic precursor. The synthetic yield was 75.30%.
The reaction formula is as follows:
TGA showed that the residual weight of the precursor at 900 ℃ under N2 was 75%. Viscosity test the surface product viscosity was 205 mpa.s.
Gel permeation chromatography tests show that the molecular weight of the obtained polycarbosilane is as follows: mn 816 and Mw 2693.
Example 3
A500 ml three-necked flask was equipped with a gas introduction piston, a sealing plug, a constant pressure dropping funnel, a condenser tube, a magnetic stirrer and a heating circulation system. All the operation processes are carried out according to Schlenk technology, and a water-free and oxygen-free system is built. 50g of boron resin was added under a flowing atmosphere, then 100g of tetrahydrofuran was added by syringe, and the temperature was raised to 40 ℃ with stirring until the dissolution was complete. Then adding 150g of liquid polycarbosilane with low molecular weight and containing alkynyl, heating to 50 ℃, continuing stirring for reaction for 10 hours, then stopping stirring, removing the oil bath, and standing for 10-20 hours. And (4) pumping out the solvent to obtain a yellow transparent oily SiBC ceramic precursor. The synthetic yield was 70.30%.
The reaction formula is as follows:
TGA showed that the residual weight of the precursor at 900 ℃ under N2 was 78%. Viscosity test the surface product viscosity was 310 mpa.s.
Gel permeation chromatography tests show that the molecular weight of the obtained polycarbosilane is as follows: mn 755, Mw 2106.
Example 4
A500 ml three-necked flask was equipped with a gas introduction piston, a sealing plug, a constant pressure dropping funnel, a condenser tube, a magnetic stirrer and a heating circulation system. All the operation processes are carried out according to Schlenk technology, and a water-free and oxygen-free system is built. 100g of boron resin was added under a flowing atmosphere, then 200g of xylene was added with a syringe, and the temperature was raised to 45 ℃ with stirring until the dissolution was complete. Then adding 150g of liquid polycarbosilane with low molecular weight containing allyl, heating to 80 ℃, continuing stirring for reaction for 10 hours, then stopping stirring, removing the oil bath, and standing for 10-20 hours. And (4) pumping out the solvent to obtain a yellow transparent oily SiBC ceramic precursor. The synthesis yield was 71.30%.
The reaction formula is as follows:
TGA showed that the residual weight of the precursor at 900 ℃ under N2 was 66%. Viscosity test the surface product viscosity was 105 mpa.s.
Gel permeation chromatography tests show that the molecular weight of the obtained polycarbosilane is as follows: mn 620, Mw 2013.
The above description is only for the best mode of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Those skilled in the art will appreciate that the invention may be practiced without these specific details.
Claims (5)
1. A boron-modified polycarbosilane resin is characterized in that: the structural formula of the boron modified polycarbosilane resin is as follows:
wherein:
r: alkynyl, propargyl or allyl;
n is a positive integer, and n is more than or equal to 1.
2. A method for producing the boron-modified polycarbosilane resin of claim 1, comprising the steps of:
adding an organic solvent into the boron resin, and then stirring at the temperature of 20-140 ℃ until the boron resin is completely dissolved to obtain a transparent solution; adding low-molecular-weight liquid polycarbosilane into the obtained transparent solution, heating and stirring for reaction, wherein the reaction temperature is 50-120 ℃, and the reaction time is 1-100 h; after the reaction is finished, cooling to room temperature, and then rotationally evaporating the organic solvent to obtain boron modified polycarbosilane resin;
the preparation reaction formula of the boron modified polycarbosilane resin is as follows:
the organic solvent is toluene, xylene, n-hexane or tetrahydrofuran;
the mass ratio of the boron resin to the organic solvent is as follows: 1: 2-10;
the mass ratio of the boron resin to the low molecular weight liquid polycarbosilane is as follows: 1: 0.5-10;
the preparation method of the low molecular weight liquid polycarbosilane comprises the following steps:
(1) adding magnesium chips into a tetrahydrofuran solvent which is purified and dried to obtain a mixed system;
(2) mixing tetrahydrofuran, unsaturated chloroalkane and chlorosilane monomers to obtain a mixed solution;
(3) dropwise adding the mixed solution obtained in the step (2) into the mixed system obtained in the step (1), stirring for 5-30 hours at the reaction temperature of-30-60 ℃ to obtain a reaction primary product;
(4) adding petroleum ether, deionized water and concentrated hydrochloric acid into the reaction primary product obtained in the step (3), controlling the reaction temperature to be-20-15 ℃, fully stirring for 0.5-5 hours, standing for 0.5-20 hours, carrying out phase separation, taking the upper organic phase, drying and carrying out rotary evaporation to obtain low-molecular-weight liquid polycarbosilane;
in the step (1), the mass ratio of the magnesium chips to the tetrahydrofuran is 1: 1-2;
in the step (2), the chlorosilane monomer is chloromethyl dichlorosilane or chloromethyl trichlorosilane; the unsaturated chloroalkane is ethynyl chloride, propargyl chloride or allyl chloride; the mass ratio of the chlorosilane monomer to the tetrahydrofuran is 1: 2-10; the mass ratio of the unsaturated chloroalkane to the chlorosilane monomer is 1: 10-20;
in the step (3), when the mixed solution is dripped into a mixed system, the mass ratio of the magnesium chips to the chlorosilane monomers is 1: 5-10;
in the step (4), petroleum ether, deionized water and concentrated hydrochloric acid are added in a volume ratio of 1: 1-10: 0.1;
in the step (4), the volume sum of the petroleum ether, the deionized water and the concentrated hydrochloric acid added and the volume ratio of the initial reaction product is 1-2: 1;
the preparation method of the boron resin comprises the following steps:
firstly, adding boron trichloride gas into purified and dried n-hexane to obtain a solution;
secondly, adding a methyl vinyl chlorosilane monomer into the solution obtained in the first step, introducing ammonia gas, stirring for 10-30 hours at the reaction temperature of-10-30 ℃, performing filter pressing on the obtained solution through a filter press, and performing rotary evaporation on the filter-pressed solution to obtain boron resin;
in the first step, the mass ratio of boron trichloride gas to n-hexane is 1: 5-8;
in the second step, the mass ratio of the methyl vinyl chlorosilane monomer to the boron trichloride is 1: 0.5-4;
in the second step, the mass ratio of the boron trichloride to the introduced ammonia gas is 1: 5-8.
3. A method of making a Si/B/C amorphous ceramic, characterized in that the method comprises the steps of: curing and pyrolyzing the boron-modified polycarbosilane resin of claim 1 to obtain an amorphous Si/B/C ceramic.
4. A method of making a Si/B/C amorphous ceramic according to claim 3 wherein: a tubular furnace is adopted during curing, and the curing system is as follows: keeping the temperature at 100 ℃ for 2h, keeping the temperature at 150 ℃ for 2h, keeping the temperature at 180 ℃ for 4h, wherein the heating rate is 1-5 ℃/min, and the curing atmosphere is inert atmosphere.
5. A method of making a Si/B/C amorphous ceramic according to claim 3 wherein: the pyrolysis process comprises the following steps: heating to 1300-1500 ℃ at a heating rate of 5-10 ℃/min under an inert atmosphere, and preserving heat for 0.5-10 h.
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| CN111573678A (en) * | 2020-05-14 | 2020-08-25 | 湖南太子新材料科技有限公司 | Silicon carbide film forming device and preparation method of silicon carbide film |
| CN114957675B (en) * | 2021-11-29 | 2023-07-21 | 中国航空制造技术研究院 | Boron modified polycarbosilane powder and preparation method thereof |
| CN114573821B (en) * | 2022-03-03 | 2023-06-09 | 上海大学 | Liquid hyperbranched polycarbosilane, preparation method and application thereof |
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| DE102008018062A1 (en) * | 2008-04-09 | 2009-10-15 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Silicon-boron-carbon-nitrogen ceramics and precursors, salt-free polymerization of RnHal3-nSi-X-BRmHal2-m |
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