CN100506891C - Preparation method of iron containing polysilazane - Google Patents
Preparation method of iron containing polysilazane Download PDFInfo
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- CN100506891C CN100506891C CNB200610011559XA CN200610011559A CN100506891C CN 100506891 C CN100506891 C CN 100506891C CN B200610011559X A CNB200610011559X A CN B200610011559XA CN 200610011559 A CN200610011559 A CN 200610011559A CN 100506891 C CN100506891 C CN 100506891C
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- methyl
- polysilazane
- vinyl
- iron containing
- iron
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Abstract
The invention discloses a making method of polysilazanyl with ferric, which is characterized by the following: adopting Fe (NR2) n and silazanyl or polysilazanyl as raw material to make the product through amino exchanging reaction; fitting for primer of Si3N4 and SiC ceramics and additive to improve high-temperature proof oxidizing property of silicon oil, silicon rubber and silicon resin.
Description
Technical field
The present invention relates to a kind of preparation method of iron containing polysilazane.
Background technology
Polysilazane is the important silicoorganic compound of a class, and its structure and polysiloxane are very close, but the formation of high molecular polysilazane is relatively more difficult.Therefore, though various silazane, ring silazane and contain other heteroatoms (silazane P) has obtained extensive studies for O, B, is that the approach that raw material obtains corresponding polysilazane is not to realize so easily with small molecules silazane and ring silazane.Meanwhile, for ferruginous organometallics, its research is less relatively, mainly concentrates on ferrocene, on iron carbonyl and the corresponding derivative thereof.Eighties of last century sixties, Germany scientist B ü ger, H. (Monatash.Chem.1963,94,1007; 1964,95,1099) at first reported M[N (SiMe
3)
2]
n(M=Cu, n=1; M=Mn, Co, Ni, n=2; M=Cr, Fe, n=3), and up to 1988, the silazane M[N (SiMe of Fe (II)
3)
2]
2Synthetic just appear in the newspapers (J.Am.Chem.Soc.1989,27,1782).And for metallic polysilazane, a series of research work has been carried out in the inventor's laboratory.CN1297956A, CN1443769A, CN1510068A disclose the inventor's the Fe that contains respectively, the patent application of Zr and Ti polysilazane and preparation method thereof.For CN1297956A disclosed " containing Fe polysilazane and synthetic method thereof ", it provides by silazane lithium salts and FeX3, and (X=Cl Br) carries out polycondensation to FeX2 and synthetic series contains Fe polysilazane and synthetic method thereof.But for the reaction between this polyfunctional group material, the product of generation is poorly soluble, and also not fusion of heating separates difficulty of purification ratio, has limited the application of this synthetic method.
Summary of the invention
The purpose of this invention is to provide a kind of by synthesizing simply the small molecules Fe (NR of convenient separation
2)
n(R=methyl, ethyl or SiR '
3, wherein R ' is a methyl, vinyl or be the mixing of the two; N=2 or 3) and silazane or polysilazane carry out amide exchange reaction and a series of preparation methods that contain the Fe polysilazane of synthetic.
Method of the present invention is with Fe (NR
2)
nThis micromolecular compound and silazane or polysilazane are raw material, prepare by amide exchange reaction and contain the Fe polysilazane, and this polymkeric substance can be used as ferruginous Si
3N
4, the SiC ceramic forerunner, also can be used as the additive of the pyro-oxidation resistance that improves various silicone oil, silicon rubber and silicone resin.
The synthetic method of iron containing polysilazane of the present invention is:
Under the protection of rare gas element, with small molecules Fe (NR
2)
n(R=methyl, ethyl or SiR '
3, wherein R ' is a methyl, vinyl or be the mixing of the two, n=2 or 3) and silazane or polysilazane be dissolved in the anhydrous organic solvent, be 60～300 ℃ of following stirring reactions in temperature of reaction, the reaction times is 0.5～100 hour, Fe (NR
2)
nBe controlled at 0.1～10 with the mass ratio of silazane or poly-silicon nitrogen; After reaction is finished, after desolventizing, distillation promptly obtains iron containing polysilazane.The state of system is that solvability is good, and the black thick liquid that heating can fused, perhaps because the variation of reaction times and raw materials quality ratio, becomes and does not dissolve and fused black solid not.
Silazane of the present invention is Me
2SiCl
2, MeHSiCl
2, MeViSiCl
2, PhMeSiCl
2Or Ph
2SiCl
2The product separated of ammonia separately, be corresponding ring silazane or small molecules silazane oligopolymer.
Me=methyl wherein, Vi=vinyl, Ph=phenyl.
Polysilazane of the present invention is Me
2SiCl
2, MeHSiCl
2, MeSiCl
3, MeViSiCl
2, ViSiCl
3, PhMeSiCl
2, Ph
2SiCl
2, PhSiCl
3, H
2SiCl
2Or HSiCl
3Ammonia hydrolysis products or ammonia hydrolysis products altogether, be have linearity, the polysilazane of ring-line structure or cross-linked structure.
Me=methyl wherein, Vi=vinyl, Ph=phenyl.
Small molecules Fe (NR of the present invention
2)
nBe Fe (NMe
2)
3, Fe (NEt
2)
3, Fe[N (SiMe
3)
2]
3, Fe[N (SiMe
2Vi)
2]
3, Fe[N (SiMeVi
2)
2]
3, Fe[N (SiVi
3)
2]
3Or their any mixture; Or Fe (NMe
2)
2, Fe (NEt
2)
2, Fe[N (SiMe
3)
2]
2, Fe[N (SiMe
2Vi)
2]
2, Fe[N (SiMeVi
2)
2]
2, Fe[N (SiVi
3)
2]
2Or their any mixture.
R=methyl wherein, ethyl or SiR '
3R ' is a methyl, vinyl or be the mixing of the two; N=2 or 3; The Me=methyl, Et=ethyl, Vi=vinyl.
Iron containing polysilazane of the present invention, when containing ferrous iron, its structural formula of iron containing polysilazane is as follows:
Wherein:
R
3For methyl, phenyl, H, vinyl or
, x=1-3.
R
1, R
2Be methyl, phenyl, H or vinyl, substituting group is identical or inequality; N=3～600.
When containing ferric iron, its structural formula of iron containing polysilazane is as follows:
Wherein:
R
3For methyl, phenyl, H, vinyl or
, x=1-3.
R
1, R
2Be methyl, phenyl, H or vinyl, substituting group is identical or inequality; N=3～600.
The used organic solvent of the present invention is aromatic hydrocarbon, tetrahydrofuran (THF), ether, pyridine, dioxane or their any mixing solutions of the alkane of 5～12 C atoms, 6～9 C atoms.
The used rare gas element of the present invention comprises nitrogen, argon gas etc.
Iron containing polysilazane provided by the present invention is at inert atmosphere, NH
3Or pyrolysis can be converted into Si/ (C)/N/Fe base ceramic material in the vacuum, can prepare corresponding ceramic powder, coating and ceramic matric composite; Also can be directly as the additive of the pyro-oxidation resistance that improves various silicone oil, silicon rubber and silicone resin.
Embodiment
Embodiment 1.
In there-necked flask, N
2Protection adds pregnancy basic ring three silazane 21.95g down, octane 100mL, and add Fe (NMe
2)
39.40g stirring at room is even, reflux is 60 hours then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane dope 26.33g of black, and productive rate is 84%.Containing the Fe amount is 10.3%.
Embodiment 2.
With mol ratio is the Me of 1:3
2SiCl
2And MeSiCl
3Ammonia is separated altogether in toluene, removes by filter NH
4Cl steams solvent, obtains a kind of polysilazane.In there-necked flask, the Ar protection adds this polysilazane 30.15g down, dimethylbenzene 100mL, and add Fe (NEt
2)
28.27g stirring at room is even, reflux is 2 hours then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane thick liquid 31.50g of black, and productive rate is 82%.Containing the Fe amount is 4.7%.
Embodiment 3.
With mol ratio is the MeHSiCl of 5:1
2And MeViSiCl
2Ammonia is separated altogether in toluene, removes by filter NH
4Cl steams solvent, obtains a kind of polysilazane.In there-necked flask, N
2Protection adds this polysilazane 10.80g down, tetrahydrofuran (THF) 100mL, and add Fe[N (SiMe
2Vi)
2]
228.27g stirring at room is even, reflux is 2 hours then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane thick liquid 28.91g of black, and productive rate is 74%.Containing the Fe amount is 7.0%.
Embodiment 4.
With H
2SiCl
2Ammonia is separated in ether, removes by filter NH
4Cl steams solvent, obtains a kind of polysilazane.In there-necked flask, the Ar protection adds this polysilazane 15.38g down, toluene 120mL, and add Fe[N (SiMe
2Vi)
2]
21.54g stirring at room is even, reflux is 0.5 hour then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane thick liquid 15.40g of black, and productive rate is 91%.Containing the Fe amount is 0.9%.
Embodiment 5.
With mol ratio is the HSiCl of 1:1
3And MeViSiCl
2Ammonia is separated altogether in toluene, removes by filter NH
4Cl steams solvent, obtains a kind of polysilazane.In there-necked flask, N
2Protection adds this polysilazane 12.43g down, dioxane 80mL, and add Fe[N (SiMeVi
2)
2]
32.49g stirring at room is even, reflux is 100 hours then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane sticky solid 10.59g of black, and productive rate is 71%.Containing the Fe amount is 1.4%.
Embodiment 6.
With mol ratio is the HSiCl of 1:1
3And MeViSiCl
2Ammonia is separated altogether in toluene, removes by filter NH
4Cl steams solvent, obtains a kind of polysilazane.In there-necked flask, the Ar protection adds this polysilazane 28.15g down, decane 60mL, and dimethylbenzene 60mL, and add Fe[N (SiMe
3)
2]
33.14g, Fe (NMe
2)
33.25g stirring at room is even, reflux is 100 hours then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane sticky solid 30.74g of black, and productive rate is 89%.Containing the Fe amount is 2.1%.
Embodiment 7.
With mol ratio is the HSiCl of 1:1
3And MeViSiCl
2Ammonia is separated altogether in dioxane, removes by filter NH
4Cl steams solvent, obtains a kind of polysilazane.In there-necked flask, N
2Protection adds this polysilazane 17.52g down, octane 50mL, and toluene 70mL, and add Fe[N (SiVi
3)
2]
23.14g stirring at room is even, reflux is 36 hours then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane sticky solid 19.21g of black, and productive rate is 93%.Containing the Fe amount is 1.5%.
Embodiment 8.
With mol ratio is the HSiCl of 2:1:1
3, Ph
2SiCl
2And PhMeSiCl
2Ammonia is separated altogether in pyridine, removes by filter NH
4Cl steams solvent, obtains a kind of polysilazane.In there-necked flask, the Ar protection adds this polysilazane 25.45g down, dioxane 40mL, and dimethylbenzene 60mL, and add Fe[N (SiMe
3)
2]
33.14g, Fe (NMe
2)
33.25g stirring at room is even, reflux is 2 hours then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane thick liquid 30.74g of black, and productive rate is 89%.Containing the Fe amount is 3.8%.
Embodiment 9.
With mol ratio is the ViSiCl of 5:1:2
3, PhSiCl
3And H
2SiCl
2Ammonia is separated altogether in toluene, removes by filter NH
4Cl steams solvent, obtains a kind of polysilazane.In there-necked flask, N
2Protection adds this polysilazane 15.38g down, toluene 50mL, and decane 50mL, and add Fe (NMe
2)
24.41g, Fe (NEt
2)
24.53g stirring at room is even, reflux is 100 hours then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane sticky solid 21.40g of black, and productive rate is 88%.Containing the Fe amount is 8.1%.
Embodiment 10.
With mol ratio is the MeViSiCl of 1:1
2And ViSiCl
3Ammonia is separated altogether in dimethylbenzene, removes by filter NH
4Cl steams solvent, obtains a kind of polysilazane.In there-necked flask, the Ar protection adds this polysilazane 2.48g down, toluene 100mL, and add Fe[N (SiMe
2Vi)
2]
322.82g stirring at room is even, reflux is 100 hours then, cools off the back removal of solvent under reduced pressure, obtains the iron containing polysilazane sticky solid 17.82g of black, and productive rate is 71%.Containing the Fe amount is 9.7%.
Claims (9)
1. the preparation method of an iron containing polysilazane is characterized in that:
Under the protection of rare gas element, with small molecules Fe (NR
2)
nBeing dissolved in the anhydrous organic solvent with silazane or polysilazane, is 60～300 ℃ of following stirring reactions in temperature of reaction, Fe (NR
2)
nBe controlled at 0.1～10 with the mass ratio of silazane or polysilazane; After reaction is finished, after desolventizing, distillation promptly obtains iron containing polysilazane;
R=methyl wherein, ethyl or SiR '
3, R ' is a methyl, vinyl or be the mixing of the two, n=2 or 3.
2. method according to claim 1 is characterized in that: described organic solvent is aromatic hydrocarbon, tetrahydrofuran (THF), ether, pyridine, dioxane or their any mixing solutions of the alkane of 5～12 C atoms, 6～9 C atoms.
3. method according to claim 1 is characterized in that: described silazane is Me
2SiCl
2, MeHSiCl
2, MeViSiCl
2, PhMeSiCl
2Or Ph
2SiCl
2The product separated of ammonia is corresponding ring silazane or small molecules silazane oligopolymer separately;
Me=methyl wherein, Vi=vinyl, Ph=phenyl.
4. method according to claim 1 is characterized in that: described polysilazane is Me
2SiCl
2, MeHSiCl
2, MeSiCl
3, MeViSiCl
2, ViSiCl
3, PhMeSiCl
2, Ph
2SiCl
2, PhSiCl
3, H
2SiCl
2Or HSiCl
3Ammonia hydrolysis products or ammonia hydrolysis products altogether, be have linearity, the polysilazane of ring-line structure or cross-linked structure;
Me=methyl wherein, Vi=vinyl, Ph=phenyl.
5. method according to claim 1 is characterized in that: when the iron in the described iron containing polysilazane was ferrous iron, the structural formula of iron containing polysilazane was:
Wherein:
R
3For methyl, phenyl, H, vinyl or
X=1-3.:
R
1, R
2Be methyl, phenyl, H or vinyl, substituting group is identical or inequality; N=3～600.
6. method according to claim 5 is characterized in that: the small molecules Fe (NR in the described preparation iron containing polysilazane raw material
2)
nBe Fe (NMe
2)
2, Fe (NEt
2)
2, Fe[N (SiMe
3)
2]
2, Fe[N (SiMe
2Vi)
2]
2, Fe[N (SiMeVi
2)
2]
2, Fe[N (SiVi
3)
2]
2Or their any mixture;
R=methyl wherein, ethyl or SiR '
3R ' is a methyl, vinyl or be the mixing of the two; The Me=methyl, Et=ethyl, Vi=vinyl.
7. method according to claim 1 is characterized in that: when the iron in the described iron containing polysilazane was ferric iron, the structural formula of iron containing polysilazane was:
Wherein:
R
3For methyl, phenyl, H, vinyl or
X=1-3.
R
1, R
2Be methyl, phenyl, H or vinyl, substituting group is identical or inequality; N=3～600.
8. method according to claim 7 is characterized in that: the small molecules Fe (NR in the described preparation iron containing polysilazane raw material
2)
nBe Fe (NMe
2)
3, Fe (NEt
2)
3, Fe[N (SiMe
3)
2]
3, Fe[N (SiMe
2Vi)
2]
3, Fe[N (SiMeVi
2)
2]
3, Fe[N (SiVi
3)
2]
3Or their any mixture;
R=methyl wherein, ethyl or SiR '
3R ' is a methyl, vinyl or be the mixing of the two; The Me=methyl, Et=ethyl, Vi=vinyl.
9. method according to claim 1 is characterized in that: described rare gas element is nitrogen or argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610011559XA CN100506891C (en) | 2006-03-24 | 2006-03-24 | Preparation method of iron containing polysilazane |
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|---|---|---|---|
| CNB200610011559XA CN100506891C (en) | 2006-03-24 | 2006-03-24 | Preparation method of iron containing polysilazane |
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| Publication Number | Publication Date |
|---|---|
| CN101041717A CN101041717A (en) | 2007-09-26 |
| CN100506891C true CN100506891C (en) | 2009-07-01 |
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| CNB200610011559XA Expired - Fee Related CN100506891C (en) | 2006-03-24 | 2006-03-24 | Preparation method of iron containing polysilazane |
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| CN106751891A (en) * | 2016-12-02 | 2017-05-31 | 镇江高美新材料有限公司 | A kind of anti-oxidant high-temperature resisting liquid silicon rubber and preparation method thereof |
| CN108675798B (en) * | 2018-08-03 | 2021-08-13 | 广东工业大学 | Silicon nitride ceramic and preparation method thereof |
| CN113388118B (en) * | 2021-03-02 | 2022-04-19 | 杭州师范大学 | Hafnium-containing multi-metal organic compound modified dimethyl silicone oil and preparation method and application thereof |
| CN113388117B (en) * | 2021-03-02 | 2022-04-19 | 杭州师范大学 | Cerium-containing multi-element metal organic compound modified dimethyl silicone oil and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0175384A2 (en) * | 1984-09-21 | 1986-03-26 | Dow Corning Corporation | Ceramic materials with increased crystallinity from silazane polymers |
| CN1297956A (en) * | 1999-11-25 | 2001-06-06 | 中国科学院化学研究所 | Polysilazane containing Fe and its synthesis |
-
2006
- 2006-03-24 CN CNB200610011559XA patent/CN100506891C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0175384A2 (en) * | 1984-09-21 | 1986-03-26 | Dow Corning Corporation | Ceramic materials with increased crystallinity from silazane polymers |
| CN1297956A (en) * | 1999-11-25 | 2001-06-06 | 中国科学院化学研究所 | Polysilazane containing Fe and its synthesis |
Non-Patent Citations (3)
| Title |
|---|
| Experimental evidence for β-methyl migration in the courseof Fe+-mediated alkane formation from silazanes in thegas phase. Sigurd Karrass and Helmut Schwarz.Organometallics,Vol.9. 1990 * |
| 新型有机硅聚合物－含铁聚硅氮烷. 李永明，任长玉，徐彩虹，谢择民.有机硅材料，第14卷第4期. 2000 * |
| 聚硅氮烷包覆纳米铁磁粉PSZFe的合成及其雷达波吸收性能研究. 刘爱祥，茹淼焱，孟凡君，张维咸，张其震，周其凤.高分子学报，第5期. 2003 * |
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| CN101041717A (en) | 2007-09-26 |
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