CN1443769A - Polysilazane containing Zr and its preparation method - Google Patents
Polysilazane containing Zr and its preparation method Download PDFInfo
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- CN1443769A CN1443769A CN 02107035 CN02107035A CN1443769A CN 1443769 A CN1443769 A CN 1443769A CN 02107035 CN02107035 CN 02107035 CN 02107035 A CN02107035 A CN 02107035A CN 1443769 A CN1443769 A CN 1443769A
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Abstract
The present invention discloses a Zr-contained polysilazane and its preparation method. Said invention provides its structure formula, and its preparation method includes the following steps: 1). drop-adding the cyclosilazane solution into the organic solution of butyl lithium, using N2 to make protection and stirring to obtain white precipitate; 2). using glass sand core pipe to press out the supernatant fluid, washing, pumping solvent to obtain white powder; 3). under the protection of N2 adding organic solvent, zirconium tetrachloride and accelerant, stirring to make reaction; 4). after the system is stratified, using glass sand core pipe to press out the supernatant fluid, washing untile the precipitate is colourless, reducing pressure and evaporating and removing solvent so as to obtain the invented product.
Description
Technical field
The present invention relates to a kind of Zr of containing polysilazane and preparation method thereof.
Background technology
Si
3N
4, the SiC pottery has the excellent high-temperature performance, high-modulus, high heat conductance and anti-oxidant, premium propertiess such as erosion resistance are widely used in fields such as machinery, chemistry, heat, electrical equipment as material and parts.Transition metal nitride, carbide such as ZrN, TiN, ZrC, TiC also demonstrate high rigidity, high-melting-point, high conductivity, performances such as high-temperature stability and erosion resistance are very potential structured materials, thereby get more and more people's extensive concerning, be applied to the wear-resistant coating field especially.If transition metal is added into Si
3N
4, among the SiC, resulting material has the advantage of the two probably concurrently, is with a wide range of applications.
The Si that contains Zr for preparation
3N
4, the SiC pottery method, bibliographical information seldom, mostly method therefor is to add Zr powder or the compound that contains Zr in the polysilazane (Dietmar Seyferth, Heinrich Lang J.Inorganic and Organometallic Polym.2 (1) 59-77 (1992); Dietmar Seyferth, Nathan Bryson J.Am.Ceram.Soc.74 (10) 2687-2689 (1991)), cracking at high temperature then.Document chlorine-containing silane and ZrCl are also arranged
4The rearrangement reaction preparation takes place under inert atmosphere contain Zr polysilane (Grish Chandra, GreggA.Zank USP 4,762,895,1988).But Zr content very low (being lower than 1%) in the resulting polymers, if as ceramic forerunner, the pottery that Pintsch process obtains is difficult to embody the performance characteristics of ZrN, ZrC.
Summary of the invention
The object of the present invention is to provide a kind of novel Zr of containing polysilazane and preparation method thereof, make it be used as the Si that contains Zr
3N
4, the SiC ceramic forerunner.We are at N
2Protection down, in the 20-800 ℃ of interval by temperature programming (2 ℃ of temperature rise rates/min), in tube furnace, presoma is carried out Pintsch process.Compare with literature method, the pottery that the presoma cracking obtains can make contained element uniform distribution on atomic level, can also prepare ceramic composite simultaneously, further improves the mechanical property of pottery.
It is the novel Zr of the containing polysilazane that raw material generates through condensation reaction with silicon-nitrogen compound lithium salts and zirconium tetrachloride that content of the present invention provides a kind of.This polymkeric substance can be used as the Si that contains Zr
3N
4, the SiC ceramic forerunner.
A kind of Zr polysilazane that contains of the present invention, its structural formula is:
R
1＝Me、Et、Ph R
2＝Me、Ph、Vi、H x＝1、2 n＝3-10
A kind of preparation method who contains the Zr polysilazane of the present invention, carry out according to following steps:
1) will encircle in the organic solution that the silazane drips of solution is added to butyllithium (n-BuLi), by weight, described consumption of organic solvent be the butyllithium consumption 5-12 doubly, N
2Protect following 10 ℃-35 ℃ to stir 1-3 hour, obtain white precipitate.
Described ring silazane comprises: encircle three silazane, cyclotetrasilazane, the substituting group on the silicon can be methyl, ethyl, phenyl, vinyl or hydrogen, and its structural formula is as follows:
R
1＝Me、Et、Ph R
2＝Me、Ph、Vi、H x＝1、2
Work as x=1, the molar ratio of described ring silazane and butyllithium is 1: 3.2-3.5;
Work as x=2, the molar ratio of described ring silazane and butyllithium is 1: 4.2-4.5.
Described ring silazane solution is meant liquid or solid-state ring silazane is dissolved in the solution of making in the organic solvent that by weight, described consumption of organic solvent is 5-12 times of ring silazane consumption.
2) extrude supernatant liquid with glass core pipe, use organic solvent washing, drain solvent and obtain white powder.
3) N
2Protection adds organic solvent, zirconium tetrachloride (ZrCl down
4) and promotor, 50 ℃-110 ℃ stirring reaction 2-3 days, by weight, consumption of organic solvent is to encircle silazane, zirconium tetrachloride (ZrCl described in the step 1
4) and the 5-12 of the total consumption of promotor doubly.Add promotor and can effectively improve productive rate.Described promotor is Tetramethyl Ethylene Diamine (TMEDA).
Work as x=1, the molar ratio of described zirconium tetrachloride, ring silazane and promotor is 3.0-3.2: 4: 0-3.2;
Work as x=2, the molar ratio of described zirconium tetrachloride, ring silazane and promotor is or 1.0-1.2: 1: 0-4.2.
4) behind the system layering, extrude supernatant liquid with glass core pipe, colourless with organic solvent washing until precipitation.Decompression 0.01-0.1Mpa, 80-120 ℃ of solvent that boils off in the clear liquid obtains the Zr of containing polysilazane of the present invention.Maximum output 93%.
Organic solvent of the present invention is C
6-C
18Alkane or aromatic hydrocarbon and straight chain or ring body ethers in arbitrary, two or three kind of mixed solvent, as toluene, normal hexane, tetrahydrofuran (THF), ether etc.Better with toluene.
The preliminary Pintsch process experiment that the present invention contains the Zr polysilazane shows that it is at N
2Ceramic yield can reach 69% in 800 ℃ of tube furnaces under the atmosphere.
Description of drawings Fig. 1 is embodiment 1 product
29(the peak ownership of 6=6.9ppm is interior mark pregnancy basic ring disilazane MM to Si NMR spectrogram
N) Fig. 2 is the FT-IR spectrogram of embodiment 1 product
Embodiment
In there-necked flask, add 15mL BuLi (2.5M), 40mL normal hexane, N
2Protection drips 2.40g pregnancy basic ring three silazane (D down
3 N) and the mixed solution of 20mL normal hexane.Drip about 40min, continue to stir standing sedimentation after 1 hour.After treating system layering, extrude supernatant liquid, drain solvent after the 20mL normal hexane washs 3 times and obtain white powder with glass core pipe.N
2Protection adds 60mL toluene and 1.94g ZrCl down
4, after reacting 2 days under 80 ℃ of stirrings, standing sedimentation.System layering, upper strata are orange red clear liquid, and lower floor is a white precipitate.Supernatant liquid is pressed onto in the clean there-necked flask toluene wash 3 times, merging filtrate with glass core pipe.The decompression 0.1MPa, 100 ℃ drain solvent after, obtain the orange red solid of 1.83g.Productive rate 59%.
The ultimate analysis data element Si C N H Zr weight percentage (%) 28.14 24.26 13.10 7.06 26.50 that contains Zr polysilazane (raw material is pregnancy basic ring three silazane) is from accompanying drawing as can be known:
29Si NMR (C
6D
6): δ=-4.26ppmFTIR (KBr pressed disc method): 2962,1255,930,795,490cm
-1
Raw material ring three silazane
29Si NMR-there is a singlet at the 4.9ppm place.Product-there is a singlet at the 4.26ppm place.The proof product structure is different with raw material, and oneself changes: because the pi-conjugated effect of p π-d makes chemical shift move to low.
Compare 1163cm in the product with raw material
-1The NH peak at place disappears, the stretching vibration peak of Si-N-Si also with the 924cm of raw material
-1Difference moves to 930cm
-1The place.In addition, 795cm
-1And 490cm
-1New absorption peak reference literature, 799cm appear in the place
-1The peak at place belongs to Si-N-Zr and absorbs 490cm
-1The peak at place belongs to Zr-N and absorbs.
Embodiment 2
Method by example 1 prepares pregnancy basic ring three silazane lithium salts 2.62g, N
2Protection adds the mixed solution 60mL and the 1.95g ZrCl of toluene, normal hexane and tetrahydrofuran (THF) (3: 1: 1) down
4, after reacting 2 days under 80 ℃ of stirrings, standing sedimentation.Supernatant liquid is pressed onto in another there-necked flask toluene wash 3 times, merging filtrate.After air distillation went out normal hexane and tetrahydrofuran (THF), decompression 0.05MPa drained solvent for 90 ℃.Obtain the orange red solid of 2.52g.Productive rate 80%.
Embodiment 3
Method by example 1 prepares pregnancy basic ring three silazane lithium salts 2.75g, N
2Protection adds 60mL toluene, 4.04g Tetramethyl Ethylene Diamine and 2.03g ZrCl down
4, after reacting 2 days under 80 ℃ of stirrings, standing sedimentation.Supernatant liquid is pressed onto in another there-necked flask toluene wash 3 times, merging filtrate.Decompression 0.01MPa drains solvent for 80 ℃, obtains the orange red solid of 3.08g.Productive rate 93%.
Embodiment 4
Get trimethyl triphenyl ring three silazane 4.48g and be dissolved in the 40mL normal hexane N
2Protection is added drop-wise in the mixed solution of 15mL BuLi (2.5M) and 40mL normal hexane down, drips about 80min, continues to stir standing sedimentation after 1 hour.After treating system layering, extrude supernatant liquid, drain solvent after the 20mL normal hexane washs 3 times and obtain white powder with glass core pipe.N
2Protection adds 60mL toluene, 3.86g Tetramethyl Ethylene Diamine and 1.94g ZrCl down
4, after reacting 2 days under 80 ℃ of stirrings, standing sedimentation.System layering, upper strata are orange red clear liquid, and lower floor is a white precipitate.Supernatant liquid is pressed onto in the clean there-necked flask toluene wash 3 times, merging filtrate with glass core pipe.Decompression 0.01MPa drains solvent for 100 ℃, obtains the orange red solid of 4.48g.Productive rate 86%.
Embodiment 5
Get hexaphenyl ring three silazane 6.51g and be dissolved in the 50mL normal hexane N
2Protection is added drop-wise in the mixed solution of 15mL BuLi (2.5M) and 40mL normal hexane down, drips about 80min, continues to stir standing sedimentation after 1 hour.After treating system layering, extrude supernatant liquid, drain solvent after the 20mL normal hexane washs 3 times and obtain white powder with glass core pipe.N
2Protection adds 60mL toluene, 3.84g Tetramethyl Ethylene Diamine and 1.94g ZrCl down
4, after reacting 2 days under 80 ℃ of stirrings, standing sedimentation.System layering, upper strata are orange red clear liquid, and lower floor is a white precipitate.Supernatant liquid is pressed onto in the clean there-necked flask toluene wash 3 times, merging filtrate with glass core pipe.Decompression 0.01MPa drains solvent for 110 ℃, obtains the orange red solid of 5.86g.Productive rate 81%.
Embodiment 6
Get prestox cyclotetrasilazane 3.21g and be dissolved in the 30mL normal hexane N
2Protection is added drop-wise in the mixed solution of 19mL BuLi (2.5M) and 40mL normal hexane down, drips about 80min, continues to stir standing sedimentation after 1 hour.After treating system layering, extrude supernatant liquid with glass core pipe, 20mL normal hexane washing 3 times is drained solvent and is obtained white powder.N
2Protection adds 60mL toluene, 5.11g Tetramethyl Ethylene Diamine and 2.57g ZrCl down
4, after reacting 2 days under 80 ℃ of stirrings, standing sedimentation.System layering, upper strata are orange red clear liquid, and lower floor is a white precipitate.Supernatant liquid is pressed onto in the clean there-necked flask toluene wash 3 times, merging filtrate with glass core pipe.Decompression 0.01MPa drains solvent for 120 ℃, obtains the orange red solid of 3.75g.Productive rate 90%.
Claims (4)
1. one kind contains the Zr polysilazane, and its structural formula is:
R
1＝Me、Et、Ph R
2＝Me、Ph、Vi、H x＝1、2 n＝3-10
2. preparation method who contains the Zr polysilazane, carry out according to following steps:
1) will encircle in the organic solution that the silazane drips of solution is added to butyllithium, by weight, described consumption of organic solvent be the butyllithium consumption 5-12 doubly, N
2Protect following 10 ℃-35 ℃ to stir 1-3 hour, obtain white precipitate;
Described ring silazane structure formula is as follows:
R
1＝Me、Et、Ph R
2＝Me、Ph、Vi、H x＝1、2
Work as x=1, the molar ratio of described ring silazane and butyllithium is 1: 3.2-3.5;
Work as x=2, the molar ratio of described ring silazane and butyllithium is 1: 4.2-4.5;
Described ring silazane solution is meant liquid or solid-state ring silazane is dissolved in the solution of making in the organic solvent that by weight, described consumption of organic solvent is 5-12 times of ring silazane consumption;
2) extrude supernatant liquid with glass core pipe, use organic solvent washing, drain solvent and obtain white powder;
3) N
2Protection adds down organic solvent, zirconium tetrachloride and promotor, 50 ℃-110 ℃ stirring reaction 2-3 days, by weight, consumption of organic solvent be described ring silazane, zirconium tetrachloride and the total consumption of promotor 5-12 doubly, described promotor is Tetramethyl Ethylene Diamine;
Work as x=1, the molar ratio of described zirconium tetrachloride, ring silazane and promotor is 3.0-3.2: 4: 0-3.2;
Work as x=2, the molar ratio of described zirconium tetrachloride, ring silazane and promotor is or 1.0-1.2: 1: 0-4.2;
4) behind the system layering, extrude supernatant liquid with glass core pipe, colourless with organic solvent washing until precipitation, decompression 0.01-0.1Mpa, 80-120 ℃ of solvent that boils off in the clear liquid obtains containing the Zr polysilazane;
The above organic solvent is C
6-C
18Alkane or aromatic hydrocarbon and straight chain or ring body ethers in arbitrary, two or three kind of mixed solvent.
3. according to the preparation method of claim 2, it is characterized in that: described organic solvent is toluene, normal hexane, tetrahydrofuran (THF), ether.
4. according to the preparation method of claim 3, it is characterized in that: described organic solvent is a toluene.
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|---|---|---|---|
| CNB021070350A CN1169814C (en) | 2002-03-08 | 2002-03-08 | Polysilazane containing Zr and its preparation method |
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|---|---|---|---|
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| Publication Number | Publication Date |
|---|---|
| CN1443769A true CN1443769A (en) | 2003-09-24 |
| CN1169814C CN1169814C (en) | 2004-10-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433551A (en) * | 2016-09-25 | 2017-02-22 | 肇庆皓明有机硅材料有限公司 | Thermal shock resistant high-refraction LED packaging glue composition and preparation method thereof |
-
2002
- 2002-03-08 CN CNB021070350A patent/CN1169814C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433551A (en) * | 2016-09-25 | 2017-02-22 | 肇庆皓明有机硅材料有限公司 | Thermal shock resistant high-refraction LED packaging glue composition and preparation method thereof |
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Granted publication date: 20041006 Termination date: 20100308 |