CN1237588A - Polysilazane whose main chain contains carbon-carbon multiple bonds and its preparation method - Google Patents
Polysilazane whose main chain contains carbon-carbon multiple bonds and its preparation method Download PDFInfo
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- CN1237588A CN1237588A CN 98102192 CN98102192A CN1237588A CN 1237588 A CN1237588 A CN 1237588A CN 98102192 CN98102192 CN 98102192 CN 98102192 A CN98102192 A CN 98102192A CN 1237588 A CN1237588 A CN 1237588A
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Abstract
The present invention relates to a polysilazane whose main chain contains carbon-carbon multiple bonds. Its structural formula is refered to in its patent specification. It is prepared by adopting the solution of 1,3-diorganohalosilicon alkyl-2,2,4,4-tetraorganocyclodisilazane and dilithium acetylite salt through the process of condensation polymerization. Said invented polysilazane possesses good thermal stability, and its preparation method is simple and its yield is up to 70-80%.
Description
The present invention relates to a kind of poly organic silicon alkane of carbon containing carbon Multiple Bonds, particularly a kind of polysilazane.
The organosilicon polymer of main chain carbon containing carbon Multiple Bonds has higher thermostability, may be as aggressiveness before high temperature material, electro-conductive material, light-guide material, the pottery, and this base polymer has many special functions.The 4th phase of polymer communication in 1979, P215-222 reported that main chain contains the silicon rubber that encircles disilazane
Under 350 ℃ warm air, still can keep the good mechanical performance, but, in the time of 400 ℃, can only use the short period of time owing to contain siloxane bond in its main chain.The existence of the 3rd phase of polymer communication in 1986 P208-213 report ring disilazane is the reason of silazane rubber main chain Heat stability is good.CHINESE JOURNAL OF POLYMERSCIENCE, 1989,7 (1), P31-37 report contain organosilicon polymer
Stability is better down at 350 ℃, but owing to contain silicon silicon key in its main chain, at 400-450 ℃, thermostability descends.
The present invention has overcome the shortcoming that duration of service is short and thermal stability descends in the prior art, and a kind of thermal stability polysilazane novel material of main chain carbon containing carbon Multiple Bonds preferably is provided.
Polysilazane of the present invention is that main chain contains the ring disilazane, contains the organosilicon polymer of carbon carbon Multiple Bonds again.
The structural formula of organosilicon polymer of the present invention is as follows:
Wherein: R
1Represent alkyl, phenyl, the naphthyl of 1-6 C atom.
R
2Represent alkyl, phenyl, the naphthyl of 1-6 C atom.
N represents the integer of 1-100
Polysilazane of the present invention is dissolved in organic solvent, and above-mentioned organic solvent is aromatic hydrocarbon, tetrahydrofuran (THF), glycol dimethyl ether, chloroform, the dimethyl sulfoxide (DMSO) of the alkane of 6-18 C atom and derivative thereof, a 6-9 carbon atom.
Polysilazane of the present invention and iodine, trinitro-fluorenone, antimony pentafluoride, tetra cyanogen subculture dimethyl benzene quinone (TCNQ) form mixture.
Above-mentioned mixture can be used as semiconductor material, electro-conductive material.
Polysilazane of the present invention is in the following order, step is prepared:
1. with 1,3-two organic radical halogenated silanes bases-2,2,4,4-having ideals, morality, culture, and discipline machine basic ring disilazane dissolves in organic solvent,
Above-mentioned organic solvent is aromatic hydrocarbon, tetrahydrofuran (THF), glycol dimethyl ether, chloroform, the dimethyl sulfoxide (DMSO) of the alkane of 6-18 C atom and derivative thereof, a 6-9 carbon atom,
2. at-90--30 ℃, be acetylene dilithium salt, disodium salt, the di-potassium and 1 of 0.5-1.5 by mole ratio, 3-two organic radical halogenated silanes bases-2,2,4, the solution of 4-having ideals, morality, culture, and discipline machine basic ring disilazane mixes, stir, kept low temperature 0.5-3 hour, and continued to be warming up to 60-160 ℃ and carry out polycondensation, the reaction times is 3-48 hour, filter, desolvate, obtain the crude product of polysilazane
3. above-mentioned crude product is through dissolving, post precipitation, and solid product obtains polysilazane of the present invention through the decompression oven dry.
The polysilazane of main chain carbon containing carbon Multiple Bonds of the present invention has good thermostability at 400-480 ℃, adopts preparation method of the present invention can obtain the polysilazane that productive rate is 70%-85%.
Embodiment 1:
Under-78 ℃, in the acetylene dilithium salt solution of 0.011mol, drip 1 of 0.01mol, 3-dimethylchlorosilane base-2,2,4, the solution of 4-tetramethyl-ring disilazane (being dissolved in the normal hexane and 10ml tetrahydrofuran (THF) mixing solutions of 10ml) reacted after 1 hour, removed low temperature and bathed, 25 ℃ were reacted down after 5 hours, after pressure reducing and steaming solvent, product are purified with normal hexane, obtain organosilicon polymer, productive rate is 72%, and Mw is 9000, and heat decomposition temperature is 414.18 ℃.
Embodiment 2:
Under-80 ℃, in the disodium acetylene salts solution of 0.01mol, drip 1 of 0.012mol, 3-diphenyl chlorosilane base-2,2,4, the solution of 4-tetramethyl-ring disilazane (being dissolved in the toluene and 10ml tetrahydrofuran (THF) mixing solutions of 10ml) reacted after 1 hour, removed low temperature and bathed, 25 ℃ are reacted after 5 hours reflux 5 hours, pressure reducing and steaming solvent down, product obtains organosilicon polymer after purifying with normal hexane, and productive rate is 70%, Mw is 11000, and heat decomposition temperature is 466.35 ℃.
Embodiment 3:
Under-60 ℃, in the acetylene dilithium salt solution of 0.010mol, drip 1 of 0.01mol, 3-diphenyl chlorosilane base-2,2,4, the solution of 4-tetraphenyl ring disilazane (being dissolved in the dimethylbenzene and 10ml tetrahydrofuran (THF) mixing solutions of 20ml) reacted after 1 hour, removed low temperature and bathed, 25 ℃ are reacted after 5 hours down, reflux 10 hours is after pressure reducing and steaming solvent, product are purified with toluene, obtain organosilicon polymer, productive rate is 81%.Mw is 11800, and heat decomposition temperature is 475.03 ℃.
Embodiment 4:
The organosilicon polymer that obtains among the embodiment 2, Mw is 8000, is dissolved in the tetrahydrofuran (THF), films.Electrode after filming and iodine are put into a vacuum drier simultaneously, and wherein iodine is placed in the small beaker, after vacuumizing, are heated to 40-60 ℃, place 5 hours, rely on the distillation infiltration of iodine, obtain the mixture that organosilicon polymer and iodine form.
The specific conductivity of measuring mixture is 10-5Scm
-1
Claims (3)
1. the polysilazane of a main chain carbon containing carbon Multiple Bonds is characterized in that the structural formula of described polysilazane is:
In the formula: R
1Be alkyl or phenyl; R
2Be alkyl or phenyl; N is the integer of 1-100.
2. the preparation method of the polysilazane of a kind of main chain carbon containing carbon Multiple Bonds according to claim 1 is characterized in that in the following order, step carries out:
1. with 1,3-two organic radical halogenated silanes bases-2,2,4,4-having ideals, morality, culture, and discipline machine basic ring disilazane dissolves in organic solvent,
2. at-90--30 ℃, be acetylene dilithium salt, disodium salt, the di-potassium and 1 of 0.5-1.5 by mole ratio, 3-two organic radical halogenated silanes bases-2,2,4, the solution of 4-having ideals, morality, culture, and discipline machine basic ring disilazane mixes,
3. be warming up to 60-160 ℃ and carry out polycondensation in 3-48 hour.
3. the preparation method of the polysilazane of a kind of main chain carbon containing carbon Multiple Bonds according to claim 2 is characterized in that described organic solvent is a normal hexane, the mixed solvent of toluene or tetrahydrofuran (THF).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98102192 CN1237588A (en) | 1998-05-29 | 1998-05-29 | Polysilazane whose main chain contains carbon-carbon multiple bonds and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98102192 CN1237588A (en) | 1998-05-29 | 1998-05-29 | Polysilazane whose main chain contains carbon-carbon multiple bonds and its preparation method |
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| CN1237588A true CN1237588A (en) | 1999-12-08 |
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| CN 98102192 Pending CN1237588A (en) | 1998-05-29 | 1998-05-29 | Polysilazane whose main chain contains carbon-carbon multiple bonds and its preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634031A (en) * | 2012-04-06 | 2012-08-15 | 中国科学院化学研究所 | Heat-resisting poly (silazane-siloxane) polymer and preparation method thereof |
| CN111662456A (en) * | 2019-03-05 | 2020-09-15 | 中国科学院化学研究所 | Preparation method of siloxane polymer |
| CN114456390A (en) * | 2022-01-26 | 2022-05-10 | 江西信达航科新材料科技有限公司 | Fluorine-containing polysilazane and preparation method thereof |
-
1998
- 1998-05-29 CN CN 98102192 patent/CN1237588A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634031A (en) * | 2012-04-06 | 2012-08-15 | 中国科学院化学研究所 | Heat-resisting poly (silazane-siloxane) polymer and preparation method thereof |
| CN111662456A (en) * | 2019-03-05 | 2020-09-15 | 中国科学院化学研究所 | Preparation method of siloxane polymer |
| CN111662456B (en) * | 2019-03-05 | 2021-08-03 | 中国科学院化学研究所 | Preparation method of siloxane polymer |
| CN114456390A (en) * | 2022-01-26 | 2022-05-10 | 江西信达航科新材料科技有限公司 | Fluorine-containing polysilazane and preparation method thereof |
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