CN102153760B - Organometallic polymer ceramic precursor, and preparation method and application thereof - Google Patents

Organometallic polymer ceramic precursor, and preparation method and application thereof Download PDF

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CN102153760B
CN102153760B CN2010105778779A CN201010577877A CN102153760B CN 102153760 B CN102153760 B CN 102153760B CN 2010105778779 A CN2010105778779 A CN 2010105778779A CN 201010577877 A CN201010577877 A CN 201010577877A CN 102153760 B CN102153760 B CN 102153760B
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ceramic precursor
luxuriantization
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王浩
陈兴波
王军
谢征芳
简科
王应德
高波
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Abstract

The invention relates to an organometallic polymer ceramic precursor, and a preparation method and application thereof. The organometallic polymer ceramic precursor is prepared by copolymerization of a double-bond-containing organometallic zirconium or titanium or hafnium monomer and a boron-containing monomer. By using the organometallic polymer ceramic precursor for preparing M(Zr,Ti,Hf)-B-C ceramic, the ceramic yield is up to 40-60%, and the content of the super-high-temperature-resistant component (ZrC/ZrB2,TiC/TiB2,HfC/HfB2) in the prepared ceramic material is higher than 70 wt%. When being treated at 2000 DEG C for 2 hours, the organometallic polymer ceramic precursor is not subjected to obvious weight loss, thereby having favorable high-temperature resistance.

Description

Organometallic polymer ceramic precursor and preparation method thereof and application
Technical field
The present invention relates to a kind of organometallic polymer ceramic precursor and preparation method thereof and application, specifically, relate to a kind of zirconocene (titanium that contains; Hafnium) organometallic polymer ceramic precursor and preparation method thereof; With and M (Zr, Ti, Hf)-application of B-C pottery preparation aspect.
Background technology
Superhigh temperature resistant pottery (Utra-high temperature ceramics; UHTCs) material is that boride, carbide with refractory metal (like Zr, Hf and Ta etc.) are one type of high temperature material of representative, in the working temperature more than 2000 ℃, can normally move use.These materials have excellent physicals; Comprise and keep good mechanical property under rare HMP, high heat conductance, high elastic coefficient and the high temperature; (S. Levine, E Opila, M. Halbig are with a wide range of applications in the high temperature resistant component in fields such as Aeronautics and Astronautics, weapons, the energy; Et al. Evaluation of ultra-high temperature ceramics for aeropropulsion use. Journal of the European Ceramic Society; 2002,22,2757-2768; Liu Jun, Xiong Xiang, Wang Jianying, Huang Baiyun. the superhigh temperature resistant investigation of materials. aerospace material technology, 2005,1,6-9; U. Kameleshwar, J. Yang, W. Hoffman. Materials for ultrahigh temperature structural application. J. Am. Ceram. Soc. Bull., 1997,76,51-56.).Compare with traditional ceramics, the superhigh temperature resistant pottery has excellent more hot strength, high-temperature creep resistance and good heat resistanceheat resistant expansion and thermal shock resistance thereof.According to over-all properties relatively, the research of superhigh temperature resistant pottery mainly concentrates on ZrC, HfC, TaC, ZrB at present 2, HfB 2, TaB 2On carbide and boride ceramics.
Powder hot-press forming process is the common methods of preparation superhigh temperature resistant pottery, and this method preparation technology is simple relatively, but also has shortcomings such as component complicacy, crystal grain undue concentration, grain-size are big, skewness.When adopting metal-powder mud dipping-pressing methods to prepare high temperature resistant ceramic matrix composite material; Owing to mud presoak not exclusively causes prepared composite material compactness relatively poor; The cavity is more more; Reuniting and hard crust can appear in the sintering process in the component skewness, is unfavorable for using.Sol-gel method is other a kind of more common method for preparing the superhigh temperature resistant pottery; But its ceramic yield lower (about 10%); Sticking liquid flowability is too poor in the preparation composite material; The infiltration pyrolysis excessive cycle, 30-40 cycle also can not reach complete densification, empty more its high temperature use properties that influences.
The precursor conversion method is the Perfected process of preparation high temperature resistant ceramic matrix composite material.It is a raw material with the organometallic polymer mainly, utilize its solvable characteristic moulding such as fusible after, make it to change inorganic ceramic material into through the elevated temperature heat disaggregating treatment from organism.This organometallic polymer just be called organic precursor method or ceramic precursor (preceramic polymer, precursor).The precursor conversion method have prepared pottery chemical constitution, microtexture, macro morphology can through molecular designing and polymer processing forming technique adjustable controlled, product purity is high, production efficiency is high, be easy to advantage such as industriallization and receive numerous material suppliers author's favor.
At present, through the ceramic subject matter of the superhigh temperature resistant of Stainless Steel via Precursor Pyrolysis be: (1) precursor solvability is relatively poor; (2) prepared superhigh temperature resistant ceramic yield is too low; (3) superhigh temperature resistant component metallic substance content is very little in the pottery.Therefore, be badly in need of one type and can be dissolved in organic solvent or can fusion, can have the ceramic precursor material of higher ceramic yield and superb pyroceramic component content again.People's public reported such as Russian Pomogailob is only arranged at present the method through vinyl polymerization prepared a kind of organometallic polymer that contains metallic element; Prepared stupalith (the D. Krutko that contains higher high temperature resistant component behind the Pintsch process; M. Borzov, D. Lemenovskii, G. Dzhardimalieva; A. Pomogailob. Synthesis and reactivity of metal-containing monomers. Part 59. Preparation and polymerization transformations of vinyl and isopropenyl derivatives of hafnocene dichloride. Russ. Chem. Bull.; Int. Ed., 2005,54; 247-251.), but its polymkeric substance ceramic conversion efficient is lower.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective that prior art exists; Provide a kind of and can be dissolved in organic solvent; Have organo-metallic M (M is Zr, Ti or Hf)-B-C polymkeric substance ceramic precursor of higher ceramic yield and superb pyroceramic component content and preparation method thereof again, use this M-B-C ceramic precursor polymer manufacture M-B-C stupalith, ceramic yield is greater than 40%; Superhigh temperature resistant component content is higher than 70% in the prepared stupalith, has the good temperature resistance ability.
The present invention's organometallic polymer ceramic precursor, its structural formula is as follows:
Figure 446006DEST_PATH_IMAGE002
Wherein
Figure 249489DEST_PATH_IMAGE004
[divinyl (or diallyl) two luxuriantization zirconiums (titanium, hafnium) below are called " A to the present invention's organometallic polymer ceramic precursor by containing two key organo-metallic zirconium (titanium, hafnium) monomers 2Monomer "] (borine or boron azane below are called " D with the boracic monomer 3Monomer ") carry out copolymerization and make.
Said A 2Monomer is to be reacted and made by dichloro two luxuriantization zirconiums (titanium, hafnium) and vinyl chlorination magnesium (perhaps propenyl chlorination magnesium), and the preparation feedback equation is as follows:
Figure 3818DEST_PATH_IMAGE006
Operation steps is: under nitrogen protection, dichloro two luxuriantization zirconiums (titanium, hafnium) being added in the there-necked flask, is solvent with the ether, is cooled to-60 oC ~-30 oC adds vinyl chlorination magnesium or propenyl chlorination magnesium, dichloro two luxuriantization zirconium (titaniums in solution; Hafnium) and the mol ratio of vinyl chlorination magnesium or propenyl chlorination magnesium between 1:2～4, regulate, isothermal reaction 24-72h, after-filtration is accomplished in reaction; Remove and desolvate; Skellysolve A flushing twice with cold with toluene-Skellysolve A recrystallization, promptly obtains A 2Monomer promptly contains two key organic zirconium (titanium, hafnium) monomers, productive rate 60-90%.
The preparation feedback equation of the present invention's organometallic polymer ceramic precursor [promptly containing zirconocene (titanium, hafnium) organometallic polymer] is shown below:
Said organometallic polymer ceramic setter preparation specifically may further comprise the steps: (1) takes by weighing raw material A 2Monomer and D 3Monomer, A 2Monomer and D 3Monomeric mol ratio is 4:1～16; (2) under nitrogen protection, with raw material A 2Monomer adds in the there-necked flask; Add solvent toluene simultaneously; (be that solid content is 20 ~ 30wt%), temperature is controlled at-18 to-30 to the add-on of solvent toluene in order to calculate 4.0 ~ 2.3 times of gained (being the Theoretical Calculation gained) organometallic polymer quality according to said reaction formula OC(preferred-20 oC); (3) with the solvent pyridine with D 3The monomer dissolving is under induction stirring, with raw material D 3Monomeric pyridine solution adds in the there-necked flask, reacts 24 ~ 50 hours (preferred 42 ~ 48 hours), becomes glutinous to reaction soln; (4) adding is equivalent to solvent toluene quality 6-10 precipitation agent Skellysolve A doubly, and deposition is filtered 80-100 oThe C oven dry removes and desolvates, and promptly obtains organometallic polymer ceramic precursor powder;
Said raw material A 2Monomer is divinyl two luxuriantization zirconiums, divinyl two luxuriantization titaniums, divinyl two luxuriantization hafniums, diallyl two luxuriantization zirconiums, diallyl two luxuriantization titaniums or diallyl two luxuriantization hafniums;
Said raw material D 3Monomer is borine or boron azane; Said raw material D 3Monomeric pyridine solution concentration is 1.8-2.2 mol/L.
Through test; Gained organometallic polymer ceramic precursor [M (Zr, Ti, Hf)-and B-C polymkeric substance ceramic precursor] dissolve in N; Dinethylformamide (DMF), n-formyl sarcolysine base pyrrolidone (NMP), DMAC N,N (DMAc) and DMSO 99.8MIN. organic solvents such as (DMSO).
Through IR, NMR and TGA etc., to M (Zr, Ti, Hf)-structure and the fundamental property of B-C ceramic precursor polymkeric substance characterize and test.
With the present invention's M (Zr, Ti, Hf)-B-C ceramic precursor polymer application is in preparation M (Zr, Ti; Hf)-B-C pottery, can adopt known precursor conversion method: with M (Zr, Ti, Hf)-B-C ceramic precursor polymkeric substance places rare gas element (nitrogen or argon gas); Cracking under the high temperature, cracking temperature are controlled at 800～1700 ℃, cracking 1～3 hour; Promptly get M (Zr, Ti, Hf)-B-C pottery.Ceramic yield 40 ~ 60%, superhigh temperature resistant component (ZrC/ZrB in the prepared stupalith 2, TiC/TiB 2, HfC/HfB 2) content is higher than 70 wt%; 2000 oC handles 2h and does not see obvious weightlessness, has the good temperature resistance ability.At aerospace, ultra sonic and reenter fields such as formula aircraft wide application prospect is arranged.
Description of drawings
Fig. 1 is the prepared superhigh temperature resistant Zr-B-C ceramic precursor polymkeric substance optical photograph of the embodiment of the invention 1;
Fig. 2 is the IR spectrogram of the prepared superhigh temperature resistant Zr-B-C ceramic precursor polymkeric substance of the embodiment of the invention 1;
Fig. 3 is the TGA spectrogram of the prepared superhigh temperature resistant Zr-B-C ceramic precursor polymkeric substance of the embodiment of the invention 1;
Fig. 4 is the prepared superhigh temperature resistant Zr-B-C pottery optical photograph of Zr-B-C ceramic precursor polymkeric substance that makes with the embodiment of the invention 1;
Fig. 5 is the XRD spectra through the prepared Zr-B-C pottery of precursor conversion method.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
One, the raw materials used zirconium organic monomer that contains of preparation Zr-B-C ceramic precursor polymkeric substance prepares reference example
The preparation of reference example 1 divinyl two luxuriantization zirconiums: 29.282g dichloro two luxuriantization zirconiums are added in the there-necked flask, add 2000 ml ether solvents, after the dissolving, be cooled to-40 oC, the vinyl grignard reagent of adding 0.2 mol in solution, isothermal reaction 48h, after-filtration is accomplished in reaction, removal of solvent under reduced pressure, the Skellysolve A flushing twice with cold with toluene-Skellysolve A recrystallization, obtains white divinyl two luxuriantization zirconiums, productive rate 70-90%.
Reference example 2 The preparation of diallyl two luxuriantization zirconiums: 29.282g dichloro two luxuriantization zirconiums are added in the there-necked flask, add 2000 ml ether solvents, after the dissolving, be cooled to-40 oC, the propenyl grignard reagent of adding 0.2 mol in solution, isothermal reaction 48h, after-filtration is accomplished in reaction, removal of solvent under reduced pressure, the Skellysolve A flushing twice with cold with toluene-Skellysolve A recrystallization, obtains white diallyl two luxuriantization zirconiums, productive rate 60-80%.
Two,Contain zirconocene, hafnium, titanium ceramic precursor polymer manufacture embodiment
Embodiment 1
Under nitrogen protection, in there-necked flask, add 0.55 g (0.002 mol) divinyl, two luxuriantization zirconium (A 2Monomer) and 5 ml toluene, homo(io)thermism is-20 oC; Under induction stirring, splash into and contain 0.02 g (0.0014 mol) borine (D 3Monomer) pyridine solution (concentration is 2.0 mol/L), reaction 48h, solution becomes is glutinous; Add Skellysolve A 100 ml, deposition, filtration, 80 oThe C oven dry obtains the faint yellow polymer powder of Zr-B-C ceramic precursor polymkeric substance (referring to Fig. 1).Productive rate 85%.
Gained Zr-B-C ceramic precursor polymkeric substance dissolves in DMF, NMP, DMAc and DMSO.Through IR, 1H NMR and TGA carry out structural characterization and test to this preceramic polymer, in IR spectrum, and 3095 cm -1With 2900 cm -1The place is respectively the hydrocarbon vibration absorption peak on the methylene radical on hydrocarbon vibration absorption peak and the main chain on the luxuriant ring of preceramic polymer, 1400 cm -1, 1100 cm -1With 800 cm -1The place corresponds to respectively on the luxuriant ring of preceramic polymer in the face hydrocarbon on the carbon-carbon double bond vibration absorption peak and luxuriant ring and out-of-plane vibration absorption peak (referring to Fig. 2).At preceramic polymer 1The chemical shift of 6.5 ppm and the 2.9 ppm places hydrogen that respectively methylene radical is corresponding in luxuriant ring hydrogen and the polymer segment in the corresponding preceramic polymer in the H NMR spectrogram.The TGA test result shows this preceramic polymer under argon gas atmosphere, 1300 oThe ceramic yield of C is 52% (referring to Fig. 3).
Zr-B-C ceramic precursor polymkeric substance is placed nitrogen, cracking under the high temperature, cracking temperature is controlled at 1400 ℃, 2 hours cracking time, promptly gets the Zr-B-C pottery, ceramic yield 50%.Superhigh temperature resistant component ZrC/ZrB in the prepared Zr-B-C stupalith 2Content 72 wt%; 2000 oC handles 2h and does not see obvious weightlessness.The optical photograph of the superhigh temperature resistant Zr-B-C pottery of use Zr-B-C ceramic precursor polymer is as shown in Figure 4, and XRD spectra is as shown in Figure 5.
Embodiment 2
WithThe difference of embodiment 1 only is, raw material A 2Monomer and D 3Monomeric mol ratio is 3:1, splashes into D 3Behind the monomeric pyridine solution, reaction 42h, surplus with embodiment 1 GainedZr-B-C ceramic precursor polymkeric substance also is the yellow polymer powder.Productive rate 89%.
Gained Zr-B-C ceramic precursor polymkeric substance dissolves in DMF, NMP, DMAc and DMSO.Zr-B-C ceramic precursor polymkeric substance is placed nitrogen, cracking under the high temperature, cracking temperature is controlled at 1300 ℃, 1.5 hours cracking time, promptly gets the Zr-B-C pottery.Ceramic yield 54%.Superhigh temperature resistant component ZrC/ZrB in the prepared Zr-B-C stupalith 2Content 73 wt%; 2000 oC handles 2h and does not see obvious weightlessness.
Embodiment 3
WithThe difference of embodiment 2 only is, raw material D 3Monomer changes the boron azane into by borine, and is surplus same Embodiment 2.
The Zr-B-C ceramic precursor polymkeric substance that makes also is yellow polymer powder, productive rate 90%.Gained Zr-B-C ceramic precursor polymkeric substance dissolves in DMF, NMP, DMAc and DMSO.Zr-B-C ceramic precursor polymkeric substance is placed nitrogen, cracking under the high temperature, cracking temperature is controlled at 1500 ℃, 1 hour cracking time, promptly gets the Zr-B-C pottery.Ceramic yield 58%.Superhigh temperature resistant component ZrC/ZrB in the prepared Zr-B-C stupalith 2Content 75 wt%; 2000 oC handles 2h and does not see obvious weightlessness.
Embodiment 4
Only be with the difference of embodiment 2, with raw material A 2Monomer changes diallyl two luxuriantization zirconiums into by divinyl two luxuriantization zirconiums, and is surplus with embodiment 2.
The Zr-B-C ceramic precursor polymkeric substance that makes also is faint yellow polymer powder, productive rate 86%.Gained Zr-B-C ceramic precursor polymkeric substance dissolves in DMF, NMP, DMAc and DMSO.Zr-B-C ceramic precursor polymkeric substance is placed nitrogen, cracking under the high temperature, cracking temperature is controlled at 1300 ℃, 2 hours cracking time, promptly gets the Zr-B-C pottery.Ceramic yield 45%.Superhigh temperature resistant component ZrC/ZrB in the prepared Zr-B-C stupalith 2Content 70 wt%; 2000 oC handles 2h and does not see obvious weightlessness.
Embodiment 5
WithThe difference of embodiment 2 only is, with raw material A 2Monomer changes divinyl two luxuriantization hafniums into by divinyl two luxuriantization zirconiums, and is surplus with embodiment 2.
The Hf that makes-B-C ceramic precursor polymkeric substance also is brown polymer powder, productive rate 80%.Gained Hf-B-C ceramic precursor polymkeric substance dissolves in DMF, NMP, DMAc and DMSO.Hf-B-C ceramic precursor polymkeric substance is placed nitrogen, cracking under the high temperature, cracking temperature is controlled at 1500 ℃, 1.5 hours cracking time, promptly gets the Hf-B-C pottery.Ceramic yield 50%.Superhigh temperature resistant component HfC/HfB in the prepared Hf-B-C stupalith 2Content 71 wt%; 2000 oC handles 2h and does not see obvious weightlessness.
Embodiment 6
WithThe difference of embodiment 2 only is, with raw material A 2Monomer changes divinyl two luxuriantization titaniums into by divinyl two luxuriantization zirconiums, and is surplus with embodiment 2.
The Ti that makes-B-C ceramic precursor polymkeric substance also is faint yellow polymer powder, productive rate 80%.Gained Ti-B-C ceramic precursor polymkeric substance dissolves in DMF, NMP, DMAc and DMSO.Ti-B-C ceramic precursor polymkeric substance is placed nitrogen, cracking under the high temperature, cracking temperature is controlled at 1400 ℃, 2 hours cracking time, promptly gets the Ti-B-C pottery.Ceramic yield 46%.Superhigh temperature resistant component TiC/TiB in the prepared Ti-B-C stupalith 2Content 73 wt%; 2000 oC handles 2h and does not see obvious weightlessness.

Claims (5)

1. organometallic polymer ceramic precursor is characterized in that structural formula is as follows:
Figure 2010105778779100001DEST_PATH_IMAGE002
Wherein
Figure DEST_PATH_IMAGE004
。
2. the preparation method of organometallic polymer ceramic precursor according to claim 1 is characterized in that, by double bond containing organometallic monomer A 2Monomer and boracic monomer D 3Monomer carries out copolyreaction and makes, and the preparation feedback equation is as follows:
Figure DEST_PATH_IMAGE006
The concrete operations step is following: (1) takes by weighing raw material A 2Monomer and D 3Monomer, A 2Monomer and D 3Monomeric mol ratio is 4:1～16; (2) under nitrogen protection, with raw material A 2Monomer adds in the there-necked flask, adds solvent toluene simultaneously, and the add-on of solvent toluene be 4.0 ~ 2.3 times according to said reaction formula calculating gained organometallic polymer quality, and temperature is controlled at-18 to-30 ℃; (3) with the solvent pyridine with D 3The monomer dissolving is under induction stirring, with raw material D 3Monomeric pyridine solution adds in the there-necked flask, reacts 24 ~ 50 hours, becomes glutinous to reaction soln; (4) adding is equivalent to solvent toluene quality 6-10 precipitation agent Skellysolve A doubly, and deposition is filtered 80-100 oThe C oven dry removes and desolvates, and promptly obtains organometallic polymer ceramic precursor powder;
Said raw material A 2Monomer is divinyl two luxuriantization zirconiums, divinyl two luxuriantization titaniums, divinyl two luxuriantization hafniums, diallyl two luxuriantization zirconiums, diallyl two luxuriantization titaniums or diallyl two luxuriantization hafniums;
Said raw material D 3Monomer is borine or boron azane.
3. according to the preparation method of the said organometallic polymer ceramic precursor of claim 2, it is characterized in that step (2), temperature are controlled at-20 ℃.
4. according to the preparation method of claim 2 or 3 said organometallic polymer ceramic precursors, it is characterized in that step (3) was reacted 42-48 hour.
5. the application of organometallic polymer ceramic precursor in preparation superhigh temperature resistant pottery according to claim 1.
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CN105218104B (en) * 2015-11-11 2018-02-27 中国人民解放军国防科学技术大学 A kind of in-situ copolymerization polymer pyrolysis method for preparing MC BN superhigh temperature ceramic materials
CN105669983B (en) * 2016-01-22 2019-02-22 中国人民解放军国防科学技术大学 One kind precursor of polymer-ceramic containing zirconium metal-organic and the preparation method and application thereof
CN105693904B (en) * 2016-03-07 2018-04-20 中国人民解放军国防科学技术大学 A kind of synthetic method of solvable ZrC Preceramic Polymers
US11873314B2 (en) * 2020-10-30 2024-01-16 Starfire Systems, Inc. Composition and preparation for hafnium carbide ceramic precursor

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