CN1629208A - Alkynyl-containing poly-siloxane and method for preparing same - Google Patents

Alkynyl-containing poly-siloxane and method for preparing same Download PDF

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CN1629208A
CN1629208A CN 200310123339 CN200310123339A CN1629208A CN 1629208 A CN1629208 A CN 1629208A CN 200310123339 CN200310123339 CN 200310123339 CN 200310123339 A CN200310123339 A CN 200310123339A CN 1629208 A CN1629208 A CN 1629208A
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alkynyl
polysilazane
organic solvent
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oligopolymer
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CN1281661C (en
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胡继东
谢择民
郑知敏
罗永明
张志杰
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Institute of Chemistry CAS
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Abstract

The invention discloses an alkynyl-containing polysiagzane with the structure of [SiR1R2(C=C-SiR1R2)*NH], wherein R1, R2 is C1-C6 alkane, alkene, phenyl or H, n=1-10, m=10-100. The alkynyl-containing polysiagzane is prepared through aminolysis method, thus has good thermally-stability and photoelectric function.

Description

A kind of alkynyl polysilazane and preparation method thereof that contains
Technical field
The present invention relates to a kind of polysilazane and preparation method thereof.
Background technology
In recent years, the research of conjugated polymers has been caused people's attention.Because they have unique electronic structure, therefore have some special performances, for example photoelectric properties can be made large-area planar indicating meter and photodiode, conductive coating, chemistry and biosensor, nonlinear optical material, luminescent material and battery etc.(Burroughes, J.H.; Brown, A.R.; Marks, R.N.Nature 1990,347, and 539), organosilicon radical is incorporated in the conjugated backbone, can improve the performance of conjugated polymers: for example in styrene polymer, introduce silicon, can be observed blue shift, changed its optical property; Organosilicon radical is incorporated in the conjugated backbone, can also improves the solvability of polymkeric substance and the workability of material.
Contain alkynyl organosilicon conjugated polymers because πDian Zi on the alkynyl and Si atom form the electron delocalization system, therefore have unique electricity and optical property.(Giseopo, K.; Toshio, M.Macromolecules 2002,35, and 4138) in addition because the introducing of alkynyl has also improved the thermostability of polymkeric substance.(Nishihara，Y.；Ando，J.；Mori，A.Macromolecules?2000，33，2779；Oshita，J.；Shinpo，A.；Kunai，A.Macromolecules?1999，32，5998；Itoh，M.；Inonue，K.；Iwata，K.；Mitsuzuka，M.；Kakigana，T.Macromolecules?1997，30，694)。Therefore, the organosilicon conjugated polymers of the siliceous alkynes of this class can be used as semiconductor material, photoelectric material, and ceramic precursor also can be used as high temperature resistant elastomerics.For example silicon alkynyl introducing siloxane polymer can be obtained a kind of linear polymer material and both have resistance to elevated temperatures, have good snappiness and workability simultaneously.(Marc，B.，Paul，P?J.；Jacques，D.Chem?Rev?1995，95，1443-1477；Armistead，J.P.；Houser，E.J.；Keller，T.M.Appl?Organometal?Chem.2000，14，253；Noriyoshi，M.；Yoshi，C.PolymerJournal?2001，33，383.)
Bibliographical information is crossed, and to contain alkynyl organosilicon conjugated polymers major part be silicon-carbon and silicon-oxygen polymer, silicon-nitrogen polymer does not also appear in the newspapers as yet, therefore our imagination is incorporated into ethynyl to have synthesized in the silazane and contains the alkynyl polysilazane, the πDian Zi of lone-pair electron on the N atom and silicon alkynes system forms big electron delocalization system, may show the optical property and the electroconductibility that make new advances.And this base polymer has stiff chain structure, also can be used as ceramic forerunner, help spinning on the one hand, can be used as reactive group on the other hand produces crosslinked under heat effect, and that the silicon-carbon fiber of existing literature method preparation is undertaken by oxidation is crosslinked, therefore helps improving ceramic yield and thermostability; Contain Si-C key and Si-N key on the main chain simultaneously, can make and contain SiC and Si in the precursor split product simultaneously 3N 4Composition forms complex phase ceramic, has better toughness; In addition, institute's this precursor of synthetic is a linear polymer, and is solvable/fusible, has good processing and storge quality before it is crosslinked.
Summary of the invention
The purpose of this invention is to provide a kind of alkynyl polysilazane and preparation method thereof that contains, institute's synthetic contains the alkynyl polysilazane and has good thermostability and photoelectric functional, can be used as ceramic forerunner, the high heat resistance photoelectric material.
A kind of structure that contains the alkynyl polysilazane provided by the present invention can be expressed as:
Figure A20031012333900041
Wherein,
R 1, R 2Be alkane, alkene, phenyl or the H of 1～6 carbon atom; Be preferably R 1, R 2Be all methyl mutually,
R 1, R 2Be all phenyl mutually, R 1Be methyl, R 2Be H, R 1Be methyl, R 2Be vinyl, or R 1Be methyl, R 2Be phenyl.
n＝1～10，m＝10～100。
Preparation method and step that the present invention contains the alkynyl polysilazane are as follows:
1) at N 2Protection down; the solution (trieline and organic solvent weight ratio are 1: 10) of trieline and organic solvent is added drop-wise in the solution of butyllithium (n-BuLi) and organic solvent (butyllithium and organic solvent weight ratio are 1: 2);-78 ℃ of following stirring reactions 12 hours, obtain acetylene lithium white casse liquid.
2) N 2Protection under agitation is added dropwise to two organic radical silicane dichloride (Me lentamente with acetylene lithium white casse liquid down 2SiCl 2, MeHSiCl 2, MeViSiCl 2, MePhSiCl 2, Ph 2SiCl 2) and the solution of organic solvent in (two organic radical silicane dichlorides and organic solvent weight ratio 1: 2～10), at-30～20 ℃ of following stirring reactions after 10～20 hours, the system standing demix, supernatant liquid shifted out adopt organic solvent washing 3～6 times, merging filtrate, decompression obtains containing alkynyl polysilazane oligopolymer after removing solvent.
3) will contain alkynyl chlorosilane oligopolymer and add organic solvent dissolution (containing alkynyl chlorosilane oligopolymer and organic solvent weight ratio 1: 10～50), feed ammonia, carry out ammonolysis reaction, under 20～140 ℃, stir after 10～36 hours, behind the system standing demix, supernatant liquid shifted out adopt organic solvent washing 3-6 time, merging filtrate, decompression remove obtain having linear structure behind the solvent contain the alkynyl polysilazane.
The poly-azane of alkynyl that contains provided by the present invention adopts gel permeation chromatography, draws n=1～10, m=10～100.
The poly-azane of alkynyl that contains provided by the present invention has good thermostability, and photoelectric functional, can be used as ceramic forerunner, the high heat resistance photoelectric material.
Embodiment
Embodiment 1
In the 250ml there-necked flask, add the 50ml tetrahydrofuran (THF), 50ml ether and 50ml (n-BuLi, 2.5mol/L), at N 2Protection down, in-78 ℃ of mixing solutionss with 36ml ether and 3.6ml trieline slowly are added drop-wise to mixing solutions in the there-necked flask.Dropwise and continue to stir 12 hours, obtain acetylene lithium white casse liquid.
In the 500ml there-necked flask, add 20ml ether and 0.1mol Me 2SiCl 2, N 2Protection slowly splashes into the muddy liquid of acetylene lithium down.Dropwise at-30 ℃ and continue stirring after 10 hours, standing sedimentation.System layering, upper strata are light yellow clear liquid, and lower floor is a white precipitate, N 2Protection is descended with the glass core supernatant liquid N 2Be depressed in the clean dried there-necked flask, precipitation is washed three times with ether.Merging filtrate.Filtrate decompression is removed and is desolvated, and obtaining containing alkynyl chlorosilane oligopolymer is light yellow thick liquid, productive rate 97%.
2g is contained alkynyl chlorosilane oligopolymer with the dissolving of 20ml toluene, 20 ℃ stir down logical ammonia gas react 10 hours down and no longer absorb ammonia to system after, logical again ammonia 2 hours.Standing sedimentation is transferred to supernatant liquid in another there-necked flask, precipitation toluene wash six times, and merging filtrate steams solvent, obtains yellow thick liquid, productive rate 85%.
The sign that contains alkynyl chlorosilane oligopolymer:
29Si-NMR(ppm)：-0.6(Cl-SiMe 2)，-40.0(C≡C-SiMe 2-C≡C)；
13C-NMR(ppm)：1.0(Si-CH 3)，112(C≡C)。
The sign that contains the alkynyl polysilazane:
Mw＝9000，Mw/Mn＝2.4；
29Si-NMR (ppm) :-16.7 ,-18.4 (HN-SiMe 2) ,-40.5 (C ≡ C-SiMe 2-C ≡ C); With contain alkynyl chlorosilane oligopolymer before ammonia is separated and compare, the displacement of Si-Cl-0.6ppm disappears ,-16.7, the new displacement peak of appearance ,-18.4ppm place illustrates that the Si-Cl key that contains alkynyl chlorosilane oligopolymer is replaced by the Si-NH key.
FTIR(cm -1)：2148(ν C≡C)，3303，1190(ν NH)，930(ν Si-NH)；
Ultimate analysis (quality %):
Calculated value: C, 53.86; H, 7.93; N, 3.49;
Measured value: C, 52.53; H, 7.93; N, 3.20.
Adopt thermal gravimetric analyzer to carry out thermogravimetic analysis (TGA), 10 ℃/min of heat-up rate, T the alkynyl polysilazane that contains that obtains Onset: 320 ℃, 1000 ℃ are residual heavy down: 60%.
Sample dissolution at THF, is made into the solution of 0.5mmol/L, adopts the F4500 fluorescence spectrophotometer that it is carried out the fluorescence emission spectrum analysis.Its maximum fluorescence emission peak is the 310nm place.
Embodiment 2
In the 500ml there-necked flask, add 50ml ether and 0.2mol MePhSiCl 2, N 2Protection slowly splashes into the muddy liquid of acetylene lithium down.Dropwise at 20 ℃ and continue stirring after 20 hours, standing sedimentation.System layering, upper strata are light yellow clear liquid, and lower floor is a white precipitate, N 2Protection is depressed into supernatant liquid in the one clean dried there-necked flask with the glass core down, and precipitation is washed six times with ether.Merging filtrate.Filtrate decompression is removed and is desolvated, and obtaining containing alkynyl chlorosilane oligopolymer is yellow thick liquid, productive rate 93%.
The sign that contains alkynyl chlorosilane oligopolymer:
29Si-NMR(ppm)：-10.0(Cl-SiMePh)，-44.0(C≡C-SiMePh-C≡C)。
2g is contained alkynyl chlorosilane oligopolymer 50ml xylene soluble, after 140 ℃ down logical ammonia stirring reactions 36 hours no longer absorb ammonia to system, logical again ammonia 2 hours.Standing sedimentation is transferred to supernatant liquid in another there-necked flask, precipitation toluene wash three times, and merging filtrate steams solvent, obtains pale brown look solid, productive rate 71%.
The sign that contains the alkynyl polysilazane:
Mw＝3900，Mw/Mn＝1.4；
29Si-NMR(ppm)：-25.0(HN-SiMePh)，-44.0(C≡C-SiMePh-C≡C)；
FTIR(cm -1)：2145(ν C≡C)，3300，1185(ν NH)，927(ν Si-NH)，3060(ν phenyl?CH)。
Adopt thermal gravimetric analyzer to carry out thermogravimetic analysis (TGA), 10 ℃/min of heat-up rate, T the alkynyl polysilazane that contains that obtains Onset: 390 ℃, 1000 ℃ are residual heavy down: 69%.
Sample dissolution at THF, is made into the solution of 0.5mmol/L, adopts the F4500 fluorescence spectrophotometer that it is carried out the fluorescence emission spectrum analysis.Its maximum fluorescence emission peak is the 360nm place.
Embodiment 3
In the 500ml there-necked flask, add 100ml ether and 0.1molPh 2SiCl 2, N 2Protection slowly splashes into the muddy liquid of acetylene lithium down.Dropwise at 0 ℃ and continue stirring after 12 hours, standing sedimentation.System layering, upper strata are orange clear liquid, and lower floor is the pink precipitation, N 2Protection is descended with the glass core supernatant liquid N 2Be depressed in the clean dried there-necked flask, precipitation is washed four times with ether.Merging filtrate.Filtrate decompression is removed and is desolvated, and obtaining containing alkynyl chlorosilane oligopolymer is brown viscous liquid, productive rate 91%.
The sign that contains alkynyl chlorosilane oligopolymer:
29Si-NMR(ppm)：-20.0(Cl-SiPh 2)，-49.0(C≡C-SiPh 2-C≡C)。
1g is contained alkynyl chlorosilane oligopolymer with the dissolving of 50ml benzene, after 80 ℃ logical ammonia stirring reactions 20 hours no longer absorb ammonia to system down, logical again ammonia 2 hours.Standing sedimentation is transferred to supernatant liquid in another there-necked flask, precipitation toluene wash four times, and merging filtrate steams solvent, obtains the orange solid, productive rate 70%.
The sign that contains the alkynyl polysilazane:
Mw＝3000，Mw/Mn＝1.4；
29Si-NMR(ppm)：-37.0，-38.5(HN-SiPh 2)，-49.0(C≡C-SiPh 2-C≡C)；
FTIR(cm -1)：2144(ν C≡C)，3296，1184(ν NH)，936(ν Si-NH)，3055(ν phenyl?CH)。
Adopt thermal gravimetric analyzer to carry out thermogravimetic analysis (TGA), 10 ℃/min of heat-up rate, T the alkynyl polysilazane that contains that obtains Onset: 447 ℃, 1000 ℃ are residual heavy down: 75%.
Sample dissolution at THF, is made into the solution of 0.5mmol/L, adopts the F4500 fluorescence spectrophotometer that it is carried out the fluorescence emission spectrum analysis.Its maximum fluorescence emission peak is the 397m place.
Embodiment 4
In the 500ml there-necked flask, add 150ml ether and 0.2mol MeHSiCl 2, N 2Protection slowly splashes into the muddy liquid of acetylene lithium down.Dropwise the back and continue stirring down after 12 hours, standing sedimentation at 0 ℃.System layering, upper strata are light yellow clear liquid, and lower floor is a white precipitate, N 2Protection is descended with the glass core supernatant liquid N 2Be depressed in the clean dried there-necked flask, precipitation is washed three times with ether.Merging filtrate.Filtrate decompression is removed and is desolvated, and obtaining containing alkynyl chlorosilane oligopolymer is yellow thick liquid, productive rate 95%.
2g is contained alkynyl chlorosilane oligopolymer with the dissolving of 100ml toluene, after 110 ℃ logical ammonia stirring reactions 36 hours no longer absorb ammonia to system down, logical again ammonia 2 hours.Standing sedimentation is transferred to supernatant liquid in another there-necked flask, precipitation toluene wash three times, and merging filtrate steams solvent, obtains yellow solid, productive rate 85%.
The sign that contains the alkynyl polysilazane:
Mw＝10000，Mw/Mn＝2.7；
FTIR(cm -1)：2140(ν C≡C)，3292，1184(ν NH)，939(ν Si-MH)，2200(ν Si-H)。
Adopt thermal gravimetric analyzer to carry out thermogravimetic analysis (TGA), 10 ℃/min of heat-up rate, T the alkynyl polysilazane that contains that obtains Onset: 300 ℃, 1000 ℃ are residual heavy down: 80%.
Embodiment 5
In the 500ml there-necked flask, add 300ml ether and 0.3mol MeViSiCl 2, N 2Protection slowly splashes into the muddy liquid of acetylene lithium down.Dropwise at 0 ℃ and continue stirring after 12 hours, standing sedimentation.System layering, upper strata are light yellow clear liquid, and lower floor is a white precipitate, N 2Protection is descended with the glass core supernatant liquid N 2Be depressed in the clean dried there-necked flask, precipitation is washed three times with ether.Merging filtrate.Filtrate decompression is removed and is desolvated, and obtaining acetylenechloride silane oligomer thing is yellow thick liquid, productive rate 90%.
The sign that contains alkynyl chlorosilane oligopolymer:
29Si-NMR(ppm)：-13.0(Cl-SiMeVi)，-48.0(C≡C-SiMeVi-C≡C)。
Contain alkynyl chlorosilane oligopolymer with the dissolving of 25ml toluene with 0.5, after 110 ℃ logical ammonia stirring reactions 24 hours no longer absorb ammonia to system down, logical again ammonia 2 hours.Standing sedimentation is transferred to supernatant liquid in another there-necked flask, precipitation toluene wash three times, and merging filtrate steams solvent, obtains the orange solid, productive rate 75%.
The sign that contains the alkynyl polysilazane:
Mw＝1000，Mw/Mn＝1.2；
29Si-NMR(ppm)：-28.0(HN-SiMeVi)，-48.0(C≡C-SiMeVi-C≡C)。
Adopt thermal gravimetric analyzer to carry out thermogravimetic analysis (TGA), 10 ℃/min of heat-up rate, T the alkynyl polysilazane that contains that obtains Onset: 350 ℃, 1000 ℃ are residual heavy down: 71%.
Sample dissolution at THF, is made into the solution of 0.5mmol/L, adopts the F4500 fluorescence spectrophotometer that it is carried out the fluorescence emission spectrum analysis.Its maximum fluorescence emission peak is the 330nm place.
Embodiment 6
In the 500ml there-necked flask, add 50ml ether and 0.1mol MeViSiCl 2, N 2Protection slowly splashes into the muddy liquid of acetylene lithium down.Dropwise at 0 ℃ and continue stirring down after 12 hours, standing sedimentation.System layering, upper strata are light yellow clear liquid, and lower floor is a white precipitate, N 2Protection is pressed supernatant liquid with the glass core down and is used N 2To a clean dried there-necked flask, precipitation is washed three times with ether.Merging filtrate.Filtrate decompression is removed and is desolvated, and obtaining containing alkynyl chlorosilane oligopolymer is yellow thick liquid, productive rate 90%.
In the 250ml there-necked flask, add 1g (NH 4) 2SO 4, the logical N of heating 2Dewater, 2g is contained alkynyl chlorosilane oligopolymer with the dissolving of 100ml toluene, join in the there-necked flask, after 110 ℃ logical ammonia stirring reactions 20 hours no longer absorb ammonia to system down, logical again ammonia 2 hours.Standing sedimentation is transferred to supernatant liquid in another there-necked flask, precipitation toluene wash three times, and merging filtrate steams solvent, obtains the orange solid, productive rate 76%.
The sign that contains the alkynyl polysilazane:
Mw＝45000，Mw/Mn＝1.6；
29Si-NMR(ppm)：-28.0(HN-SiMeVi)，-48.0(C≡C-SiMeVi-C≡C)。
Adopt thermal gravimetric analyzer to carry out thermogravimetic analysis (TGA), 10 ℃/min of heat-up rate, T the alkynyl polysilazane that contains that obtains Onset: 360 ℃, 1000 ℃ are residual heavy down: 71%.
Sample dissolution at THF, is made into the solution of 0.5mmol/L, adopts the F4500 fluorescence spectrophotometer that it is carried out the fluorescence emission spectrum analysis.Its maximum fluorescence emission peak is the 343nm place.

Claims (3)

1, a kind of alkynyl polysilazane that contains is characterized in that the described alkynyl polysilazane that contains has following structure:
Wherein,
R 1, R 2Be alkane, alkene, phenyl or the H of 1～6 carbon atom; R 1, R 2Be all methyl mutually, R 1, R 2Be all phenyl mutually, R 1Be methyl, R 2Be H, R 1Be methyl, R 2Be vinyl, or R 1Be methyl, R 2Be phenyl, n=1～10, m=10～100.
2, the described preparation method who contains the alkynyl polysilazane of claim 1 is characterized in that being undertaken by following step:
1) at N 2Protection is that mixed dissolution after to be added drop-wise to butyllithium and organic solvent at 1: 10 be in 1: 2 blended solution by weight with trieline and organic solvent by weight down ,-78 ℃ of following stirring reactions 12 hours, obtains acetylene lithium white casse liquid,
2) N 2Protection under agitation is added dropwise to two organic radical silicane dichloride Me lentamente with acetylene lithium white casse liquid down 2SiCl 2, MeHSiCl 2, MeViSiCl 2, MePhSiCl 2Or Ph 2SiCl 2Respectively with organic solvent in 1: 2～10 blended solution, at-30～20 ℃ of following stirring reactions after 10～20 hours, the system standing demix, supernatant liquid shifted out adopt organic solvent washing 3～6 times, merging filtrate, decompression obtains containing alkynyl polysilazane oligopolymer after removing solvent
3) the synthetic alkynyl polysilazane that contains
To contain alkynyl chlorosilane oligopolymer and organic solvent behind 1: 10～50 mixed dissolutions, feed ammonia, carry out ammonolysis reaction, at 20～140 ℃ of following stirring reactions after 10～36 hours, behind the system standing demix, supernatant liquid shifted out adopt organic solvent washing 3-6 time, merging filtrate, decompression obtains containing the alkynyl polysilazane after removing solvent.
3, the preparation method who contains the alkynyl polysilazane according to claim 2 is characterized in that described organic solvent is the aromatic hydrocarbon of 6～8 carbon atoms, tetrahydrofuran (THF) and ether, or their mixed solvent.
CN 200310123339 2003-12-17 2003-12-17 Alkynyl-containing poly-siloxane and method for preparing same Expired - Fee Related CN1281661C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
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CN101235113B (en) * 2008-01-04 2010-04-14 华东理工大学 Aryne resin containing polysilicone and preparation method thereof
CN110683852A (en) * 2019-10-12 2020-01-14 航天材料及工艺研究所 Low-cost ceramic-based thermostructural composite material and preparation method thereof
CN114456389A (en) * 2022-01-26 2022-05-10 江西信达航科新材料科技有限公司 Modified organic polysilazane and preparation method thereof
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
CN114561016A (en) * 2022-03-14 2022-05-31 江西信达航科新材料科技有限公司 Benzenepolysilazane and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101235113B (en) * 2008-01-04 2010-04-14 华东理工大学 Aryne resin containing polysilicone and preparation method thereof
CN110683852A (en) * 2019-10-12 2020-01-14 航天材料及工艺研究所 Low-cost ceramic-based thermostructural composite material and preparation method thereof
CN114456389A (en) * 2022-01-26 2022-05-10 江西信达航科新材料科技有限公司 Modified organic polysilazane and preparation method thereof
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
CN114561016A (en) * 2022-03-14 2022-05-31 江西信达航科新材料科技有限公司 Benzenepolysilazane and preparation method thereof
CN114561016B (en) * 2022-03-14 2022-12-30 江西信达航科新材料科技有限公司 Benzenepyridazoline and preparation method thereof

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