CN103044312A - Carbon decaborane containing polyimide monomer and preparation method thereof - Google Patents
Carbon decaborane containing polyimide monomer and preparation method thereof Download PDFInfo
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- CN103044312A CN103044312A CN2012104835237A CN201210483523A CN103044312A CN 103044312 A CN103044312 A CN 103044312A CN 2012104835237 A CN2012104835237 A CN 2012104835237A CN 201210483523 A CN201210483523 A CN 201210483523A CN 103044312 A CN103044312 A CN 103044312A
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Abstract
The invention discloses a carbon decaborane containing polyimide monomer and a preparation method thereof. A synthetic route is provided. The heat resistance of the carbon decaborane containing polyimide monomer structure is remarkably improved, and weight loss of the monomer at 1000 DEG C is just 8.08% and that of the monomer at 500 DEG C is 21.94%.
Description
Technical field
The present invention relates to a kind of polyimide monomer and preparation thereof that contains the carbon Decaboron tetradecahydride.
Background technology:
Polyimide material can use wide territory temperature (200 ℃-400 ℃) is stable, has corrosion-resistant, high-strength and high-modulus, high thermostability, and service temperature is about 400 ℃, and aerospace field is badly in need of the polyimide material of higher service temperature at present.
The carbon Decaboron tetradecahydride is the compound that is formed icosahedron electron deficiency cage structure by 2 carbon atoms and 10 boron atoms, has " energy measuring tank " effect, adjacent group had shielding effect, has high thermostability, the introducing of carborane group can improve the resistance toheat of polymkeric substance, introduce main chain or the side chain of polymkeric substance, can significantly improve the resin resistance toheat.Resistance toheat can improve more than 100 ℃ in introducing main chain, and thermotolerance can improve more than 50 ℃ in the introducing side chain, therefore, carborane is introduced in the polyimide monomer structure, is the resistance toheat effective way that improves polyimide resin.
Summary of the invention:
The technical problem that the present invention solves is intended to improve the resistance to elevated temperatures of polyimide, has designed and synthesized and has contained the carbon Decaboron tetradecahydride with the polyimide monomer of acetylene bond structural unit.
A kind of polyimide monomer that contains carbon Decaboron tetradecahydride structure is provided among the present invention, and its structural formula is as follows:
The present invention also provides a kind of described synthetic method that contains the polyimide monomer of carbon Decaboron tetradecahydride structure, and synthesis path is as shown below:
This polyimide monomer structure resistance toheat that contains the carborane structure is significantly improved: 1000 ℃ of weightlessness only are that 8.08%, 1500 ℃ of weightlessness is 21.94%.
Description of drawings
Fig. 1 is the TG collection of illustrative plates that contains the polyimide monomer of carborane structure provided by the invention;
Fig. 2 is Compound C
1The H-NMR spectrogram;
Fig. 3 is Compound C
1The mass spectrum of H-NMR;
Fig. 4 is Compound D
1The H-NMR spectrogram.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples.Unless otherwise, each step below among each embodiment all is to carry out at normal temperatures and pressures.
Synthesizing of example 1 Compound C:
Get the 3.08g compd A, 1.14g compd B, 10mL DMF lead to nitrogen at 140-160 ℃ of stirring reaction in three-necked bottle, react to stop after 6 hours.Separate out solid after being down to room temperature, suction filtration, filter cake water and ethyl acetate are washed, and vacuum-drying obtains faint yellow solid 2.86g Compound C (productive rate is mass percent 96.62%).Compound C
1The H-NMR spectrogram is seen Fig. 2.
1H-NMR (400MHz, CDCl
3) δ 8.009 (s, 2H), 7.870 (S, 4H), 73597-7.579 (m, 4H), (7.427-7.414 m, 6H), 4.470 (s, 4H). ultimate analysis (measured value): C:78.46%, H:3.703%, N:5.099%, theoretical value: C:79.401%, H:3.702%, N:5.144%., mass spectrum: 544.5(M), as shown in Figure 3.
Synthesizing of example 2 Compound D:
Get the 0.5g Compound C, 0.18g acetonitrile borine, 30mL toluene is in three-necked bottle, logical nitrogen temperature to 100 ℃ under the normal temperature, react stopped reaction after 10 hours, be down to normal temperature, filter, the filter residue washed with dichloromethane obtains white solid product 0.03g Compound D (the productive rate mass percent is 8.54%) through the column chromatography separation.The Compound D fusing point: 147.5 ℃,
1H-NMR (400MHz, CDCl
3) δ 8.040(s, 1H), 7.981-7.978 (m, 1H), (7.928-7.877 m, 3H), 7.728-7.708 (m, 1H), (7.612-7.588 m, 2H), 7.498-7.477 (m, 2H), (7.439-7.421 m, 3H), 7.325-7.285 (m, 1H), (7.249-7.211 m, 2H), 4.911 (s, 4H), 2.276 (Br s, 20H) Compound D
1The H-NMR spectrogram is seen Fig. 4, and the TG collection of illustrative plates is seen Fig. 1.
Claims (5)
1. polyimide monomer, its structural formula is as follows:
2. the polyimide monomer of a carbon containing Decaboron tetradecahydride structure, its structural formula is as follows:
3. synthetic method that contains the polyimide monomer of carbon Decaboron tetradecahydride structure, synthesis path is as follows:
4. a kind of synthetic method that contains the polyimide monomer of carbon Decaboron tetradecahydride structure according to claim 3, wherein Compound C is synthetic as follows:
Get compd A, compd B, DMF lead to nitrogen at 140-160 ℃ of stirring reaction in three-necked bottle, react to stop after 6 hours; Separate out solid after being down to room temperature, suction filtration, filter cake water and ethyl acetate are washed, and vacuum-drying obtains faint yellow solid, i.e. Compound C.
5. a kind of synthetic method that contains the polyimide monomer of carbon Decaboron tetradecahydride structure according to claim 3, wherein Compound D is synthetic as follows:
Get Compound C, acetonitrile borine, toluene are in three-necked bottle, and logical nitrogen temperature to 100 ℃ under the normal temperature react stopped reaction after 10 hours, is down to normal temperature, filters, and the filter residue washed with dichloromethane obtains white solid product, i.e. Compound D through the column chromatography separation.
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| CN201210483523.7A CN103044312B (en) | 2012-11-26 | 2012-11-26 | Carbon decaborane containing polyimide monomer and preparation method thereof |
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| CN103044312A true CN103044312A (en) | 2013-04-17 |
| CN103044312B CN103044312B (en) | 2015-06-17 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881091A (en) * | 2014-03-15 | 2014-06-25 | 西南石油大学 | Preparation method of polyimide containing carborane structure |
| CN104945627A (en) * | 2015-07-28 | 2015-09-30 | 中国工程物理研究院总体工程研究所 | Method for preparing ultra-high heat resistant polyimide polymer |
| CN105585588A (en) * | 2015-12-29 | 2016-05-18 | 北京航空航天大学 | Carborane-containing organic matter, PET (polyethylene terephthalate) as neutron radiation protection material as well as preparation thereof |
| CN107759478A (en) * | 2016-08-16 | 2018-03-06 | 北京航空航天大学 | A kind of Thermocurable polyimide material and preparation method and application containing double carboranes |
| CN110698670A (en) * | 2019-10-31 | 2020-01-17 | 中国科学院化学研究所 | Carborane modified polyimide film and preparation method thereof |
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| US5817744A (en) * | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881091A (en) * | 2014-03-15 | 2014-06-25 | 西南石油大学 | Preparation method of polyimide containing carborane structure |
| CN103881091B (en) * | 2014-03-15 | 2016-04-27 | 西南石油大学 | A kind of preparation method of the polyimide containing carborane structure |
| CN104945627A (en) * | 2015-07-28 | 2015-09-30 | 中国工程物理研究院总体工程研究所 | Method for preparing ultra-high heat resistant polyimide polymer |
| CN104945627B (en) * | 2015-07-28 | 2018-04-24 | 中国工程物理研究院总体工程研究所 | It is a kind of to prepare the method with superelevation heat resistant poly imide polymer |
| CN105585588A (en) * | 2015-12-29 | 2016-05-18 | 北京航空航天大学 | Carborane-containing organic matter, PET (polyethylene terephthalate) as neutron radiation protection material as well as preparation thereof |
| CN105585588B (en) * | 2015-12-29 | 2017-08-15 | 北京航空航天大学 | Organic matter and neutron radiation protection material polyester and its preparation containing carborane |
| CN107759478A (en) * | 2016-08-16 | 2018-03-06 | 北京航空航天大学 | A kind of Thermocurable polyimide material and preparation method and application containing double carboranes |
| CN107759478B (en) * | 2016-08-16 | 2020-07-14 | 北京航空航天大学 | Thermosetting polyimide material containing dicarboborane, preparation method and application |
| CN110698670A (en) * | 2019-10-31 | 2020-01-17 | 中国科学院化学研究所 | Carborane modified polyimide film and preparation method thereof |
| CN110698670B (en) * | 2019-10-31 | 2024-01-23 | 中国科学院化学研究所 | Carborane modified polyimide film and preparation method thereof |
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| CN103044312B (en) | 2015-06-17 |
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